U.S. patent number 7,375,108 [Application Number 10/564,013] was granted by the patent office on 2008-05-20 for 2-substituted pyrimidines.
This patent grant is currently assigned to BASF Aktiengesellschaft. Invention is credited to Carsten Blettner, Markus Gewehr, Wassilios Grammenos, Thomas Grote, Andreas Gypser, Bernd Muller, Joachim Rheinheimer, Peter Schafer, Maria Scherer, Frank Schieweck, Ulrich Schofl, Anja Schwogler, Reinhard Stierl, Siegfried Strathmann, Jordi Tormo i Blasco, Oliver Wagner.
United States Patent |
7,375,108 |
Schwogler , et al. |
May 20, 2008 |
2-substituted pyrimidines
Abstract
The invention relates to 2-substituted pyrimidines of the
formula I ##STR00001## in which the index n and the substituents
R.sup.1 to R.sup.3 and L are as defined in the description and
R.sup.4 corresponds to one of the formulae ##STR00002## in which
R.sup.a, X and R.sup.b are as defined in the description; and also
to processes for preparing these compounds, to pesticidal
compositions comprising these compounds and to their use as
pesticides.
Inventors: |
Schwogler; Anja (Mannheim,
DE), Gewehr; Markus (Kastellaun, DE),
Muller; Bernd (Frankenthal, DE), Grote; Thomas
(Wachenheim, DE), Grammenos; Wassilios (Ludwigshafen,
DE), Tormo i Blasco; Jordi (Laudenbach,
DE), Gypser; Andreas (Mannheim, DE),
Rheinheimer; Joachim (Ludwigshafen, DE), Blettner;
Carsten (Mannheim, DE), Schafer; Peter
(Ottersheim, DE), Schieweck; Frank (Hessheim,
DE), Wagner; Oliver (Neustadt, DE), Stierl;
Reinhard (Freinsheim, DE), Schofl; Ulrich (Bruhl,
DE), Strathmann; Siegfried (Limburgerhof,
DE), Scherer; Maria (Godramstein, DE) |
Assignee: |
BASF Aktiengesellschaft
(Ludwigshafen, DE)
|
Family
ID: |
34117367 |
Appl.
No.: |
10/564,013 |
Filed: |
July 15, 2004 |
PCT
Filed: |
July 15, 2004 |
PCT No.: |
PCT/EP2004/007877 |
371(c)(1),(2),(4) Date: |
January 09, 2007 |
PCT
Pub. No.: |
WO2005/012261 |
PCT
Pub. Date: |
February 10, 2005 |
Prior Publication Data
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Document
Identifier |
Publication Date |
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US 20070105873 A1 |
May 10, 2007 |
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Foreign Application Priority Data
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Jul 24, 2003 [DE] |
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103 33 857 |
Dec 9, 2003 [DE] |
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103 57 714 |
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Current U.S.
Class: |
514/256;
544/329 |
Current CPC
Class: |
C07D
239/42 (20130101) |
Current International
Class: |
C07D
239/42 (20060101); A01N 43/54 (20060101) |
Field of
Search: |
;544/329 ;514/256 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
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2 467 683 |
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May 2003 |
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CA |
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WO-01/96314 |
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Dec 2001 |
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WO |
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WO-02/074753 |
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Sep 2002 |
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WO |
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WO-03/043993 |
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May 2003 |
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WO |
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Primary Examiner: Rao; Deepak
Attorney, Agent or Firm: Birch, Stewart, Kolasch &
Birch, LLP
Claims
We claim:
1. A 2-substituted pyrimidine of the formula I ##STR00036## in
which the index and the substituents are as defined below: n is an
integer from 1 to 5; L is halogen, cyano, cyanato (OCN),
C.sub.1-C.sub.8-alkyl, C.sub.2-C.sub.8-alkenyl,
C.sub.2-C.sub.8-alkynyl, C.sub.1-C.sub.6-alkoxy,
C.sub.2-C.sub.8-alkenyloxy, C.sub.2-C.sub.8-alkynyloxy,
C.sub.3-C.sub.6-cycloalkyl, C.sub.4-C.sub.6-cycloalkenyl,
C.sub.3-C.sub.6-cycoalkyloxy, C.sub.4-C.sub.6-cycloalkenyloxy,
nitro, --C(.dbd.O)-A, --C(.dbd.O)--O-A, --C(.dbd.O)--N(A')A,
C(A')(=N--OA), N(A')A, N(A')-C(.dbd.O)-A, N(A'')-C(.dbd.O)--N(A')A,
S(.dbd.O).sub.m-A, S(.dbd.O).sub.m--O-A or S(.dbd.O).sub.m--N(A')A,
m is 0, 1 or 2; A, A', A'' independently of one another are
hydrogen, C.sub.1-C.sub.6-alkyl, C.sub.2-C.sub.6-alkenyl,
C.sub.2-C.sub.6-alkynyl, C.sub.3-C.sub.8-cycloalkyl,
C.sub.3-C.sub.8-cycloalkenyl, phenyl, where the organic radicals
may be partially or fully halogenated or may be substituted by
nitro, cyanato, cyano or C.sub.1-C.sub.4-alkoxy; or A and A'
together with the atoms to which they are attached are a five- or
six-membered saturated, partially unsaturated or aromatic
heterocycle which contains one to four heteroatoms from the group
consisting of O, N and S; where the aliphatic groups of the radical
definitions of L for their part may be partially or fully
halogenated or may carry one to four groups R.sup.u; R.sup.u is
cyano, C.sub.1-C.sub.6-alkoxy, C.sub.3-C.sub.6-cycloalkyl,
C.sub.2-C.sub.8-alkenyloxy, C.sub.2-C.sub.8-alkynyloxy,
C.sub.4-C.sub.6-cycloalkenyl, C.sub.3-C.sub.6-cycloalkyloxy,
C.sub.4-C.sub.6-cycloalkenyloxy, --C(.dbd.O)-A, --C(.dbd.O)--O-A,
--C(.dbd.O)--N(A')A, C(A')(=N--OA), N(A')A, N(A')-C(.dbd.O)-A,
N(A'')-C(.dbd.O)--N(A')A, S(.dbd.O).sub.m-A, S(.dbd.O).sub.m--O-A
or S(.dbd.O).sub.m--N(A')A; R.sup.1,R.sup.2 independently of one
another are C.sub.1-C.sub.6-alkyl, C.sub.2-C.sub.6-alkenyl,
C.sub.2-C.sub.6-alkynyl, C.sub.3-C.sub.6-cycloalkyl, or
C.sub.3-C.sub.6-halocycloalkyl, where the aliphatic group of the
radical definitions of R.sup.1 and R.sup.2 for their part may be
partially or fully halogenated or may carry one to four groups
R.sup.v: R.sup.v is cyano, C.sub.3-C.sub.6-cycloalkyl,
C.sub.4-C.sub.6-cycloalkenyl, hydroxyl, C.sub.1-C.sub.6-alkoxy,
C.sub.2-C.sub.8-alkenyloxy, C.sub.2-C.sub.8-alkynyloxy,
C.sub.3-C.sub.6-cycloalkyloxy, C.sub.4-C.sub.6-cycloalkenyloxy,
C.sub.1-C.sub.6-alkylthio, --C(.dbd.O)-A, --C(.dbd.O)--O-A,
--C(.dbd.O)--N(A')A, C(A')(=N--OA), N(A')A, N(A')-C(.dbd.O)-A,
N(A'')-C(.dbd.O)--N(A')A, S(.dbd.O).sub.m-A, S(.dbd.O).sub.m--O-A
or S(.dbd.O).sub.m--N(A')A or phenyl, where the phenyl moiety may
carry one to three radicals selected from the group consisting of:
halogen, C.sub.1-C.sub.6-alkyl, C.sub.2-C.sub.6-alkenyl,
C.sub.2-C.sub.6-alkynyl, C.sub.3-C.sub.6-cycloalkyl,
C.sub.1-C.sub.6-haloalkyl, C.sub.1-C.sub.6-alkoxy, cyano, nitro,
--C(.dbd.O)-A, --C(.dbd.O)--O-A, --C(.dbd.O)--N(A')A,
C(A')(-N--OA), N(A')A; or R.sup.2 may additionally be hydrogen; or
R.sup.1 and R.sup.2 may also, together with the nitrogen atom to
which they are attached, form a saturated or unsaturated five- or
six-membered ring which may be interrupted by an ether (--O--),
carbonyl (C.dbd.O), thio (--S--), sulfoxyl (--S[.dbd.O]--) or
sulfenyl (--SO.sub.2--) or a further amino (--N(R.sup.a) group,
where R.sup.a is hydrogen or C.sub.1-C.sub.6-alkyl, and/or may
contain one or more substituents from the group consisting of
halogen, C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-haloalkyl and
oxy-C.sub.1-C.sub.3-alkyleneoxy; R.sup.3 is halogen, cyano,
C.sub.1-C.sub.4-alkyl, C.sub.2-C.sub.4-alkenyl,
C.sub.2-C.sub.4-alkynyl, C.sub.3-C.sub.6-cycloalkyl,
C.sub.1-C.sub.4-alkoxy, C.sub.3-C.sub.4-alkenyloxy,
C.sub.3-C.sub.4-alkynyloxy, C.sub.1-C.sub.6-alkylthio,
di-(C.sub.1-C.sub.6-alkyl)amino or C.sub.1-C.sub.6-alkylamino,
where the alkyl, alkenyl and alkynyl radicals of R.sup.3 may be
substituted by halogen, cyano, nitro, C.sub.1-C.sub.2-alkoxy or
C.sub.1-C.sub.4-alkoxycarbonyl; R.sup.4 corresponds to one of the
formulae ##STR00037## where X is a direct bond, --(C.dbd.O)--,
--(C.dbd.O)--NH--, --(C.dbd.O)--O--, --O--, --NR.sup.c--,
--CH.sub.2O--(C.dbd.O)--, --CH.dbd.CH--(C.dbd.O)--, where in each
case the left moiety is attached to the nitrogen atom; R.sup.a is
hydrogen, C.sub.1-C.sub.6-alkyl, C.sub.2-C.sub.8-alkenyl,
C.sub.2-C.sub.8-alkynyl or benzyl; R.sup.b is hydrogen,
C.sub.1-C.sub.6-alkyl, C.sub.2-C.sub.6-alkenyl or
C.sub.2-C.sub.8-alkynyl; R.sup.c is hydrogen,
C.sub.1-C.sub.6-alkyl, C.sub.2-C.sub.6-alkenyl,
C.sub.2-C.sub.8-alkynyl, benzyl or C.sub.1-C.sub.6-acyl, where the
aliphatic, alicyclic or aromatic groups of the radical definitions
of R.sup.a, R.sup.b and/or R.sup.c for their part may carry one to
four groups R.sup.w: R.sup.w is halogen, cyano, OR.sup.x,
NHR.sup.x, SR.sup.x, C.sub.1-C.sub.6-alkyl,
C.sub.2-C.sub.6-alkenyl, C.sub.2-C.sub.6-alkynyl,
C.sub.1-C.sub.6-alkoxy, C.sub.1-C.sub.4-alkoxycarbonyl,
C.sub.1-C.sub.4-acylamino, [1,3]dioxolane-C.sub.1-C.sub.4-alkyl,
[1,3]dioxane-C.sub.1-C.sub.4-alkyl, where R.sup.x is hydrogen,
C.sub.1-C.sub.6-alkyl, C.sub.2-C.sub.8-alkenyl,
C.sub.2-C.sub.8-alkynyl or benzyl.
2. The 2-substituted pyrimidine of the formula I as claimed in
claim 1 in which the index and the substituents are as defined
below: n is an integer from 1 to 3, where at least one substituent
L is located in the ortho-position on the phenyl ring; L is
halogen, cyano, methyl, methoxy, --C(.dbd.O)--O-A,
--C(.dbd.O)--N(A')A, C(A')(=N--OA), N(A')A, N(A')-C(.dbd.O)-A, A,A'
independently of one another are hydrogen, C.sub.1-C.sub.6-alkyl,
C.sub.2-C.sub.6-alkenyl, C.sub.2-C.sub.6-alkynyl, phenyl, where the
organic radicals may be partially or fully halogenated or may be
substituted by C.sub.1-C.sub.4-alkoxy; or A and A' together with
the atoms to which they are attached are a five- or six-membered
saturated heterocycle which contains one or two heteroatoms from
the group consisting of O, N and S; where the aliphatic groups of
the radical definitions of L for their part may be partially or
fully halogenated; R.sup.1,R.sup.2 independently of one another are
C.sub.1-C.sub.6-alkyl, C.sub.2-C.sub.6-alkenyl,
C.sub.2-C.sub.6-alkynyl, C.sub.1-C.sub.6-haloalkyl,
C.sub.2-C.sub.6-haloalkenyl or C.sub.2-C.sub.6-haloalkynyl; R.sup.2
may additionally be hydrogen; R.sup.1 and R.sup.2 may also,
together with the nitrogen atom to which they are attached, form a
saturated or unsaturated five- or six-membered ring which may be
interrupted by an ether (--O--) or a further amino (--N(R.sup.a)
group, where R.sup.a is hydrogen or C.sub.1-C.sub.6-alkyl, and/or
may contain one or more substituents from the group consisting of
halogen, C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-haloalkyl and
oxy-C.sub.1-C.sub.3-alkyleneoxy; R.sup.3 is halogen, cyano,
C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-alkoxy or
C.sub.1-C.sub.4-haloalkyl; R.sup.4 corresponds to one of the
formulae ##STR00038## where X is a direct bond, --(C.dbd.O)--,
--(C.dbd.O)--NH--, --(C.dbd.O)--O--, --O--, --NR.sup.c--, where in
each case the left moiety is attached to the nitrogen atom; R.sup.a
is hydrogen, methyl, allyl or propargyl; R.sup.b is hydrogen,
C.sub.1-C.sub.4-alkyl, allyl or propargyl; R.sup.c is hydrogen,
methyl or C.sub.1-C.sub.4-acyl, where the aliphatic groups of the
radical definitions of R.sup.a, R.sup.b and/or R.sup.c for their
part may carry one or two groups R.sup.w: R.sup.w is halogen,
OR.sup.x, NHR.sup.x, C.sub.1-C.sub.6-alkyl,
C.sub.1-C.sub.4-alkoxycarbonyl, C.sub.1-C.sub.4-acylamino,
[1,3]dioxolane-C.sub.1-C.sub.4-alkyl,
[1,3]dioxane-C.sub.1-C.sub.4-alkyl, where R.sup.x is hydrogen,
methyl, allyl or propargyl.
3. The 2-substituted pyrimidine as claimed in claim 1 in which
R.sup.3 is chlorine, cyano, methyl or methoxy.
4. The 2-substituted pyrimidine as claimed in claim 1 in which
R.sup.4 corresponds to a formula ##STR00039## where X is a direct
bond, --O-- or --(C.dbd.O)--O--, and R.sup.a is hydrogen or
C.sub.1-C.sub.6-alkyl.
5. The 2-substituted pyrimidine as claimed in claim 1 in which the
phenyl group substituted by L.sub.n is the group B ##STR00040##
where # is the point of attachment to the pyrimidine skeleton and
L.sup.1 is fluorine, chlorine, CH.sub.3 or CF.sub.3; L.sup.2,
L.sup.4 independently of one another are hydrogen, CH.sub.3 or
fluorine; L.sup.3 is hydrogen, fluorine, chlorine, cyano, CH.sub.3,
SCH.sub.3, OCH.sub.3, SO.sub.2CH.sub.3, NH--C(.dbd.O)CH.sub.3,
N(CH.sub.3)--C(.dbd.O)CH.sub.3 or COOCH.sub.3 and L.sup.5 is
hydrogen, fluorine, chlorine or CH.sub.3.
6. A process for preparing the compounds IA by hydrolysis
##STR00041## of the nitriles of the formula IV, where the
substituents R.sup.1, R.sup.2, R.sup.3 and L and the index n are as
defined in claim 1, which comprises carrying out the hydrolysis in
the presence of a base and hydrogen peroxide.
7. A process for preparing the compounds IA' and IC according to
the invention where the substituents L.sub.n, R.sup.1, R.sup.2,
R.sup.3, X, R.sup.a and R.sup.b are as defined in claim 1, which
process uses nitriles of the formula IV ##STR00042## which are
converted with alcohols of the formula R'OH, where R' is
C.sub.1-C.sub.8-alkyl, C.sub.2-C.sub.8-alkenyl,
C.sub.2-C.sub.8-alkynyl or C.sub.3-C.sub.6-cycloalkyl, where the
radicals alkyl, alkenyl and alkynyl may be partially or fully
halogenated and may carry one to three groups R.sup.v, into the
esters of the formula V, which are then, using amines
R.sup.a--X--NH.sub.2 and added dehydrating agents, converted into
the amides IA' and thither, in the presence of carbon tetrahalide
and triarylphosphine, into the imine halides of the formula VI and
finally, with alcohols of the formula R.sup.bOH and bases, into the
imino ethers of the formula IC.
8. An ester of the formula V ##STR00043## in which the substituents
are as defined below: n is an integer from 1 to 5; L is halogen,
cyano, cyanato (OCN), C.sub.1-C.sub.8-alkyl,
C.sub.2-C.sub.8-alkenyl, C.sub.2-C.sub.8-alkynyl,
C.sub.1-C.sub.6-alkoxy, C.sub.2-C.sub.8-alkenyloxy,
C.sub.2-C.sub.8-alkynyloxy, C.sub.3-C.sub.6-cycloalkyl,
C.sub.4-C.sub.6-cycloalkenyl, C.sub.3-C.sub.6-cycoalkyloxy,
C.sub.4-C.sub.6-cycloalkenyloxy, nitro, --C(.dbd.O)-A,
--C(.dbd.O)--O-A, --C(.dbd.O)--N(A')A, C(A')(=N--OA), N(A')A,
N(A')-C(.dbd.O)-A, N(A'')-C(.dbd.O)--N(A')A, S(.dbd.O).sub.m-A,
S(.dbd.O).sub.m--O-A or S(.dbd.O).sub.m--N(A')A, m is 0, 1 or 2; A,
A', A'' independently of one another are hydrogen,
C.sub.1-C.sub.6-alkyl, C.sub.2-C.sub.6-alkenyl,
C.sub.2-C.sub.6-alkynyl, C.sub.3-C.sub.8-cycloalkyl,
C.sub.3-C.sub.8-cycloalkenyl, phenyl, where the organic radicals
may be partially or fully halogenated or may be substituted by
nitro cyanato cyano or C.sub.1-C.sub.4-alkoxy; or A and A' together
with the atoms to which the are attached are a five- or
six-membered saturated, partially unsaturated or aromatic
heterocycle which contains one to four heteroatoms from the group
consisting of O, N and S; where the aliphatic groups of the radical
definitions of L for their part may be partially or fully
halogenated or may carry one to four groups R.sup.u; R.sup.2 is
cyano, C.sub.1-C.sub.6-alkoxy, C.sub.3-C.sub.6-cycloalkyl,
C.sub.2-C.sub.8-alkenyloxy, C.sub.2-C.sub.8-alkynyloxy,
C.sub.4-C.sub.6-cycloalkenyl, C.sub.3-C.sub.6-cycloalkyloxy,
C.sub.4-C.sub.6-cycloalkenyloxy, --C(.dbd.O)-A, --C(.dbd.O)--O-A,
--C(.dbd.O)--N(A')A, C(A')(=N--OA), N(A')A, N(A')-C(.dbd.O)-A,
N(A'')-C(.dbd.O)--N(A')A, S(.dbd.O).sub.m-A, S(.dbd.O).sub.m--O-A
or S(.dbd.O).sub.m--N(A')A; R.sup.1,R.sup.2 independently of one
another are C.sub.1-C.sub.6-alkyl, C.sub.2-C.sub.6-alkenyl,
C.sub.2-C.sub.6-alkynyl, C.sub.3-C.sub.6-cycloalkyl, or
C.sub.3-C.sub.6-halocycloalkyl, where the aliphatic group of the
radical definitions of R.sup.1 and R.sup.2 for their part may be
partially or fully halogenated or may carry one to four groups
R.sup.v: R.sup.v is cyano, C.sub.3-C.sub.6-cycloalkyl,
C.sub.4-C.sub.6-cycloalkenyl, hydroxyl, C.sub.1-C.sub.6-alkoxy,
C.sub.2-C.sub.8-alkenyloxy, C.sub.2-C.sub.8-alkynyloxy,
C.sub.3-C.sub.6-cycloalkyloxy, C.sub.4-C.sub.6-cycloalkenyloxy,
C.sub.1-C.sub.6-alkylthio, --C(.dbd.O)-A, --C(.dbd.O)--O-A,
--C(.dbd.O)--N(A')A, C(A')(=N--OA), N(A')A, N(A')-C(.dbd.O)-A,
N(A'')-C(.dbd.O)--N(A')A, S(.dbd.O).sub.m-A, S(.dbd.O).sub.m--O-A
or S(.dbd.O).sub.m--N(A'')A or phenyl, where the phenyl moiety may
carry one to three radicals selected from the group consisting of:
halogen, C.sub.1-C.sub.6-alkyl, C.sub.2-C.sub.6-alkenyl,
C.sub.2-C.sub.6-alkynyl, C.sub.3-C.sub.6-cycloalkyl,
C.sub.1-C.sub.6-haloalkyl, C.sub.1-C.sub.6-alkoxy, cyano, nitro,
--C(.dbd.O)-A, --C(.dbd.O)--O-A, --C(.dbd.O)--N(A')A,
C(A')(-N--OA), N(A')A; or R.sup.2 additionally be hydrogen; or
R.sup.1 and R.sup.2 may also, together with the nitrogen atom to
which they are attached, form a saturated or unsaturated five- or
six-membered ring which may be interrupted by an ether (--O--),
carbonyl (C.dbd.O), thio (--S--), sulfoxyl (--S[.dbd.O]--) or
sulfenyl (--SO.sub.2--) or a further amino (--N(R.sup.a) group,
where R.sup.a is hydrogen or C.sub.1-C.sub.6-alkyl, and/or may
contain one or more substituents from the group consisting of
halogen, C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-haloalkyl and
oxy-C.sub.1-C.sub.3-alkyleneoxy; R.sup.3 is halogen, cyano,
C.sub.1-C.sub.4-alkyl, C.sub.2-C.sub.4-alkenyl,
C.sub.2-C.sub.4-alkynyl, C.sub.3-C.sub.6-cycloalkyl,
C.sub.1-C.sub.4-alkoxy, C.sub.3-C.sub.4-alkenyloxy,
C.sub.3-C.sub.4-alkynyloxy, C.sub.1-C.sub.6-alkylthio,
di-(C.sub.1-C.sub.6-alkyl)amino or C.sub.1-C.sub.6-alkylamino,
where the alkyl, alkenyl and alkynyl radicals of R.sup.3 may be
substituted by halogen, cyano, nitro, C.sub.1-C.sub.2-alkoxy or
C.sub.1-C.sub.4-alkoxycarbonyl; R' is C.sub.1-C.sub.8-alkyl,
C.sub.2-C.sub.8-alkenyl, C.sub.2-C.sub.8-alkynyl or
C.sub.3-C.sub.6-cycloalkyl, where the radicals alkyl, alkenyl and
alkynyl may be partially or fully halogenated and may carry one to
three groups R.sup.v.
9. The ester as claimed in claim 8 where R' is isopropyl.
10. An imine halide of the formula VI ##STR00044## where the
substituents are as defined below: n is an integer from 1 to 5; L
is halogen, cyano, cyanato (OCN), C.sub.1-C.sub.8-alkyl,
C.sub.2-C.sub.8-alkenyl, C.sub.2-C.sub.8-alkynyl,
C.sub.1-C.sub.6-alkoxy, C.sub.2-C.sub.8-alkenyloxy,
C.sub.2-C.sub.8-alkynyloxy, C.sub.3-C.sub.6-cycloalkyl,
C.sub.4-C.sub.6-cycloalkenyl, C.sub.3-C.sub.6-cycoalkyloxy,
C.sub.4-C.sub.6-cycloalkenyloxy, nitro, --C(.dbd.O)-A,
--C(.dbd.O)--O-A, --C(.dbd.O)--N(A')A, C(A')(=N--OA), N(A')A,
N(A')-C(.dbd.O)-A, N(A'')-C(.dbd.O)--N(A')A, S(.dbd.O).sub.m-A,
S(.dbd.O).sub.m--O-A or S(.dbd.O).sub.m--N(A')A, m is 0, 1 or 2; A,
A', A'' independent of one another are hydrogen,
C.sub.1-C.sub.6-alkyl, C.sub.2-C.sub.6-alkenyl,
C.sub.2-C.sub.6-alkynyl, C.sub.3-C.sub.8-cycloalkyl,
C.sub.3-C.sub.8-cycloalkenyl, phenyl, where the organic radicals
may be partially or fully halogenated or may be substituted by
nitro, cyanato, cyano or C.sub.1-C.sub.4-alkoxy; or A and A'
together with the atoms to which they are attached are a five- or
six-membered saturated, partially unsaturated or aromatic
heterocycle which contains one to four heteroatoms from the group
consisting of O, N and S; where the aliphatic groups of the radical
definitions of L for their part may be partially or fully
halogenated or may carry one to four groups R.sup.u; R.sup.u is
cyano, C.sub.1-C.sub.6-alkoxy C.sub.3-C.sub.6-cycloalkyl,
C.sub.2-C.sub.8-alkenyloxy, C.sub.2-C.sub.8-alkynyloxy,
C.sub.4-C.sub.6-cycloalkenyl, C.sub.3-C.sub.6-cycloalkyloxy,
C.sub.4-C.sub.6-cycloalkenyloxy, --C(.dbd.O)-A, --C(.dbd.O)--O-A,
--C(.dbd.O)--N(A')A, C(A')(=N--OA), N(A')A, N(A')-C(.dbd.O)-A,
N(A'')-C(.dbd.O)--N(A')A, S(.dbd.O).sub.mA, S(.dbd.O).sub.m--O-A or
S(.dbd.O).sub.m--N(A')A; R.sup.1,R.sup.2 independently of one
another are C.sub.1-C.sub.6-alkyl, C.sub.2-C.sub.6-alkenyl,
C.sub.2-C.sub.6-alkynyl, C.sub.3-C.sub.6-cycloalkyl, or
C.sub.3-C.sub.6-halocycloalkyl, where the aliphatic group of the
radical definitions of R.sup.1 and R.sup.2 for their part may be
partially or fully halogenated or may carry one to four groups
R.sup.v: R.sup.v is cyano, C.sub.3-C.sub.6-cycloalkyl,
C.sub.4-C.sub.6-cycloalkenyl, hydroxyl, C.sub.1-C.sub.6-alkoxy,
C.sub.2-C.sub.8-alkenyloxy, C.sub.2-C.sub.8-alkynyloxy,
C.sub.3-C.sub.6-cycloalkyloxy, C.sub.4-C.sub.6-cycloalkenyloxy,
C.sub.1-C.sub.6-alkylthio, --C(.dbd.O)-A, --C(.dbd.O)--O-A,
--C(.dbd.O)--N(A')A, C(A')(=N--OA'), N(A')A, N(A')-C(.dbd.O)-A,
N(A'')-C(.dbd.O)--N(A')A, S(.dbd.O).sub.m-A, S(.dbd.O).sub.m--O-A
or S(.dbd.O).sub.m--N(A')A or phenyl, where the phenyl moiety may
carry one to three radicals selected from the group consisting of:
halogen, C.sub.1-C.sub.6-alkyl, C.sub.2-C.sub.6-alkenyl,
C.sub.2-C.sub.6-alkynyl, C.sub.3-C.sub.6-cycloalkyl,
C.sub.1-C.sub.6-haloalkyl, C.sub.1-C.sub.6-alkoxy, cyano, nitro,
--C(.dbd.O)-A, --C(.dbd.O)--O-A, --C(.dbd.O)--N(A')A,
C(A')(-N--OA), N(A')A; or R.sup.2 may additionally be hydrogen; or
R.sup.1 and R.sup.2 may also, together with the nitrogen atom to
which they are attached, form a saturated or unsaturated five- or
six-membered ring which may be interrupted by an ether (--O--),
carbonyl (C.dbd.O), thio (--S--), sulfoxyl (--S[.dbd.O]--) or
sulfenyl (--SO.sub.2--) or a further amino (--N(R.sup.a) group,
where R.sup.a is hydrogen or C.sub.1-C.sub.6-alkyl, and/or may
contain one or more substituents from the group consisting of
halogen, C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-haloalkyl and
oxy-C.sub.1-C.sub.3-alkyleneoxy; R.sup.3 is halogen, cyano,
C.sub.1-C.sub.4-alkyl, C.sub.2-C.sub.4-alkenyl,
C.sub.2-C.sub.4-alkynyl, C.sub.3-C.sub.6-cycloalkyl,
C.sub.1-C.sub.4-alkoxy, C.sub.3-C.sub.4-alkenyloxy,
C.sub.3-C.sub.4-alkynyloxy, C.sub.1-C.sub.6-alkylthio,
di-(C.sub.1-C.sub.6-alkyl)amino or C.sub.1-C.sub.6-alkylamino,
where the alkyl, alkenyl and alkynyl radicals of R.sup.3 may be
substituted by halogen, cyano, nitro, C.sub.1-C.sub.2-alkoxy or
C.sub.1-C.sub.4-alkoxycarbonyl; X is a direct bond, --(C.dbd.O)--,
--(C.dbd.O)--NH--, --(C.dbd.O)--O--, --O--, --NR.sup.c--,
--CH.sub.2O--(C.dbd.O)--, --CH.dbd.CH--(C.dbd.O)--, where in each
case the left moiety is attached to the nitrogen atom; R.sup.a is
hydrogen C.sub.1-C.sub.6-alkyl, C.sub.2-C.sub.8-alkenyl,
C.sub.2-C.sub.8-alkynyl or benzyl; and Hal is fluorine, chlorine,
bromine or iodine.
11. A pesticide which comprises a solid or liquid carrier and a
compound of the formula I as claimed in claim 1.
12. A pesticide which comprises a solid or liquid carrier and a
compound of the formula V as claimed in claim 8.
13. A method for controlling phytopathogenic harmful fungi, which
comprises treating the fungi or the materials, plants, the soil or
the seeds to be protected against fungal attack with an effective
amount of a compound of the formula I as claimed in claim 1.
14. A method for controlling phytopathogenic harmful fungi, which
comprises treating the fungi or the materials, plants, the soil or
the seeds to be protected against fungal attack with an effective
amount of a compound of the formula V as claimed claim 8.
Description
The invention relates to 2-substituted pyrimidines of the formula
I
##STR00003## in which the index and the substituents are as defined
below: n is an integer from 1 to 5; L is halogen, cyano, cyanato
(OCN), C.sub.1-C.sub.8-alkyl, C.sub.2-C.sub.8-alkenyl,
C.sub.2-C.sub.8-alkynyl, C.sub.1-C.sub.6-alkoxy,
C.sub.2-C.sub.8-alkenyloxy, C.sub.2-C.sub.8-alkynyloxy,
C.sub.3-C.sub.6-cycloalkyl, C.sub.4-C.sub.6-cycloalkenyl,
C.sub.3-C.sub.6-cycoalkyloxy, C.sub.4-C.sub.6-cycloalkenyloxy,
nitro, --C(.dbd.O)-A, --C(.dbd.O)--O-A, --C(.dbd.O)--N(A')A,
C(A')(=N--OA), N(A')A, N(A')-C(.dbd.O)-A, N(A'')-C(.dbd.O)--N(A')A,
S(.dbd.O).sub.m-A, S(.dbd.O).sub.m--O-A or S(.dbd.O).sub.m--N(A')A,
m is 0, 1 or 2; A, A', A'' independently of one another are
hydrogen, C.sub.1-C.sub.6-alkyl, C.sub.2-C.sub.6-alkenyl,
C.sub.2-C.sub.6-alkynyl, C.sub.3-C.sub.8-cycloalkyl,
C.sub.3-C.sub.8-cycloalkenyl, phenyl, where the organic radicals
may be partially or fully halogenated or may be substituted by
nitro, cyanato, cyano or C.sub.1-C.sub.4-alkoxy; or A and A'
together with the atoms to which they are attached are a five- or
six-membered saturated, partially unsaturated or aromatic
heterocycle which contains one to four heteroatoms from the group
consisting of O, N and S; where the aliphatic groups of the radical
definitions of L for their part may be partially or fully
halogenated or may carry one to four groups R''; R.sup.u is cyano,
C.sub.1-C.sub.6-alkoxy, C.sub.3-C.sub.6-cycloalkyl,
C.sub.2-C.sub.8-alkenyloxy, C.sub.2-C.sub.8-alkynyloxy,
C.sub.4-C.sub.6-cycloalkenyl, C.sub.3-C.sub.6-cycloalkyloxy,
C.sub.4-C.sub.6-cycloalkenyloxy, --C(.dbd.O)-A, --C(.dbd.O)--O-A,
--C(.dbd.O)--N(A')A, C(A')(=N--OA), N(A')A, N(A')-C(.dbd.O)-A,
N(A'')-C(.dbd.O)--N(A')A, S(.dbd.O).sub.m-A, S(.dbd.O).sub.m--O-A
or S(.dbd.O).sub.m--N(A')A; R.sup.1,R.sup.2 independently of one
another are C.sub.1-C.sub.6-alkyl, C.sub.2-C.sub.6-alkenyl,
C.sub.2-C.sub.6-alkynyl, C.sub.3-C.sub.6-cycloalkyl,
C.sub.3-C.sub.6-halocycloalkyl, where the aliphatic groups of the
radical definitions of R.sup.1 and R.sup.2 for their part may be
partially or fully halogenated or may carry one to four groups
R.sup.v: R.sup.v is cyano, C.sub.3-C.sub.6-cycloalkyl,
C.sub.4-C.sub.6-cycloalkenyl, hydroxyl, C.sub.1-C.sub.6-alkoxy,
C.sub.2-C.sub.8-alkenyloxy, C.sub.2-C.sub.8-alkynyloxy,
C.sub.3-C.sub.6-cycloalkyloxy, C.sub.4-C.sub.6-cycloalkenyloxy,
C.sub.1-C.sub.6-alkylthio, --C(.dbd.O)-A, --C(.dbd.O)--O-A,
--C(.dbd.O)--N(A')A, C(A')(=N--OA), N(A')A, N(A')-C(.dbd.O)-A,
N(A'')-C(.dbd.O)--N(A')A, S(.dbd.O).sub.m-A, or
S(.dbd.O).sub.m--O-A or S).dbd.O).sub.m--N(A')A or phenyl, where
the phenyl moiety may carry one to three radicals selected from the
group consisting of: halogen, C.sub.1-C.sub.6-alkyl,
C.sub.2-C.sub.6-alkenyl, C.sub.2-C.sub.6-alkynyl,
C.sub.3-C.sub.6-cycloalkyl, C.sub.1-C.sub.6-haloalkyl,
C.sub.1-C.sub.6-alkoxy, cyano, nitro, --C(.dbd.O)-A,
--C(.dbd.O)--O-A, --C(.dbd.O)--N(A')A, C(A')(=N--OA), N(A')A;
R.sup.2 may additionally be hydrogen; R.sup.1 and R.sup.2 may also,
together with the nitrogen atom to which they are attached, form a
saturated or unsaturated five- or six-membered ring which may be
interrupted by an ether (--O--), carbonyl (C.dbd.O), thio (--S--),
sulfoxyl (--S[.dbd.O]--) or sulfenyl (--SO.sub.2--) or a further
amino (--N(R.sup.a) group, where R.sup.a is hydrogen or
C.sub.1-C.sub.6-alkyl, and/or may contain one or more substituents
from the group consisting of halogen, C.sub.1-C.sub.6-alkyl,
C.sub.1-C.sub.6-haloalkyl and oxy-C.sub.1-C.sub.3-alkyleneoxy;
R.sup.3 is halogen, cyano, C.sub.1-C.sub.4-alkyl,
C.sub.2-C.sub.4-alkenyl, C.sub.2-C.sub.4-alkynyl,
C.sub.3-C.sub.6-cycloalkyl, C.sub.1-C.sub.4-alkoxy,
C.sub.3-C.sub.4-alkenyloxy, C.sub.3-C.sub.4-alkynyloxy,
C.sub.1-C.sub.6-alkylthio, di-(C.sub.1-C.sub.6-alkyl)amino or
C.sub.1-C.sub.6-alkylamino, where the alkyl, alkenyl and alkynyl
radicals of R.sup.3 may be substituted by halogen, cyano, nitro,
C.sub.1-C.sub.2-alkoxy or C.sub.1-C.sub.4-alkoxycarbonyl; R.sup.4
corresponds to one of the formulae
##STR00004## where X is a direct bond, --(C.dbd.O)--,
--(C.dbd.O)--NH--, --(C.dbd.O)--O--, --O--, --NR.sup.c--,
--CH.sub.2O--(C.dbd.O)--, --C.dbd.C--(C.dbd.O)--, where in each
case the left atom of the bridge is attached to the nitrogen atom;
R.sup.a is hydrogen, C.sub.1-C.sub.6-alkyl,
C.sub.2-C.sub.8-alkenyl, C.sub.2-C.sub.8-alkynyl or benzyl; R.sup.b
is hydrogen, C.sub.1-C.sub.6-alkyl, C.sub.2-C.sub.6-alkenyl or
C.sub.2-C.sub.6-alkynyl; R.sup.c is hydrogen,
C.sub.1-C.sub.6-alkyl, C.sub.2-C.sub.6-alkenyl,
C.sub.2-C.sub.6-alkynyl, benzyl or C.sub.1-C.sub.6-acyl, where the
aliphatic, alicyclic or aromatic groups of the radical definitions
of R.sup.a, R.sup.b and/or R.sup.c for their part may carry one to
four groups R.sup.w: R.sup.w is halogen, cyano, OR.sup.x,
NHR.sup.x, SR.sup.x, C.sub.1-C.sub.6-alkyl,
C.sub.2-C.sub.6-alkenyl, C.sub.2-C.sub.6-alkynyl,
C.sub.1-C.sub.6-alkoxy, C.sub.1-C.sub.4-alkoxycarbonyl,
C.sub.1-C.sub.4-acylamino, [1,3]dioxolane-C.sub.1-C.sub.4-alkyl,
[1,3]dioxane-C.sub.1-C.sub.4-alkyl, where R.sup.x is hydrogen,
C.sub.1-C.sub.6-alkyl, C.sub.2-C.sub.8-alkenyl,
C.sub.2-C.sub.8-alkynyl or benzyl.
Moreover, the invention relates to a process for preparing these
compounds, to compositions comprising 2-pyrimidines and to their
use for controlling phytopathogenic harmful fungi.
Fungicidal pyrimidines carrying a cyanamino substituent in the
2-position are known from WO-A 01/96314. Furthermore, fungicidal
2-pyrimidyl-N-methoxyamidines are known from WO-A 03/43993.
However, in many cases the activity of the abovementioned
pyrimidines is unsatisfactory. It is an object of the present
invention to provide compounds having improved activity.
We have found that this object is achieved by the pyrimidines of
the formula I defined at the outset. Moreover, we have found
processes for their preparation and compositions comprising them
for controlling harmful fungi.
The compounds I can be obtained by different routes. 1) It is
possible, for example, to use sulfones of the formula 11 whose
preparation is described in detail in WO-A 02/074753 or DE
10156279.9 as starting materials. Reaction of the sulfones II with
metal cyanides III (Me.sup.+CN.sup.-) yields the nitriles IV. Metal
cyanides are to be understood as meaning primarily alkali metal
cyanides or alkaline earth metal cyanides or else covalent
cyanides, such as tin tetracyanide.
##STR00005##
The exchange of the sulfonate group for the nitrile group is
carried out by methods known from the literature, as described, for
example, in WO-A 03/043993.
The further synthesis can be carried out as shown in Scheme 1:
##STR00006##
The nitrile compound IV can be hydrolyzed to the amide IA under
acidic or, preferably, basic conditions. The hydrolysis is carried
out, for example, under the conditions described by Katritzky et
al. in Synthesis 1989, pp. 949-950 (hydrogen peroxide, base, polar
aprotic solvent). Hydrolyses of nitriles to amides under acidic
conditions are described in Comprehensive Organic Chemistry, Vol 2,
Sutherland, I.O. Pergamon Press, Oxford, 1979, p. 964.
Alternatively, the Pinner adduct, which is generated when in
general hydrochloric acid forms an adduct with nitrile IV, can be
reacted with an alcohol of the formula R.sup.bOH, where R.sup.b is
as defined above, to give the imino ether of the formula IB. The
alkylation with R.sup.aX--Y, where R.sup.a and the bridge X are as
defined above and y is a leaving group such as halide, sulfate or
sulfonate, gives compounds of type IC.
The alkylation with R.sup.a--Y starting with compound IB or the
nitrile IV can also be carried out using Meerwein salts of the
formula (R.sup.a).sub.3OBF.sub.4 analogously to the procedures
given in Synth. Commun., 1983, 13, p. 753 or Helv. Chim. Acta,
1986, 69, p. 1224. This affords compounds I in which X is a direct
bond.
An alternative synthesis of the compounds IA according to the
invention is shown in Scheme 2.
##STR00007##
The synthesis, shown in Scheme 2, of the compounds IA' and IC in
turn uses nitrile IV as starting material. The nitrile IV can
preferably be prepared under acidic conditions in the presence of
alcohols of the formula R'OH, where R' is C.sub.1-C.sub.8-alkyl,
C.sub.2-C.sub.8-alkenyl, C.sub.2-C.sub.8-alkynyl or
C.sub.3-C.sub.6-cycloalkyl, where the radicals alkyl, alkenyl and
alkynyl may be partially or fully halogenated and may carry one to
three groups R.sup.v. The reaction of V with amines to give the
amides IA' can be carried out as described in Org. Lett., 2001, Vol
3, p. 1053-56 or in J. Org. Chem., 2000, Vol 85, p. 8415-20. The
subsequent reaction with Meerwein salts of the formula
(R.sup.b).sub.3OBF.sub.4 analogously to the procedures given in
Synth. Commun., 1983, 13, p. 753 or Helv. Chim. Acta, 1986, 69, p.
1224 yields the compounds of the formula IC according to the
invention. The imine halides of the formula VI where Hal is halogen
and in particular chlorine or bromine can be obtained analogously
to Synthesis, 1991, Vol 9, p. 750-752. In an Appel reaction using,
for example, carbon tetrabromide and triphenylphosphine, the
corresponding bromine compounds are prepared. The latter can
finally be reacted with alcohols of the formula R.sup.bOH and base
to give the compounds IC according to the invention.
The radical R.sup.3 (in particular alkyl) in the 6-position on the
pyrimidine ring can be introduced by reaction with transition metal
catalysis, such as Ni or Pd catalysis. In some cases it may be
advisable to change the order and to introduce the substituent
R.sup.3 prior to the substituent NR.sup.1R.sup.2.
##STR00008##
In the formula (R.sup.3).sub.y-wX.sub.w-M.sup.y, M is a metal ion
of valency Y, such as, for example, B, Zn, Mg, Cu or Sn, X is
chlorine, bromine, iodine or hydroxy, R.sup.3 is preferably
C.sub.1-C.sub.4-alkyl and w is a number from 0 to 3. This reaction
can be carried out, for example, analogously to the following
methods: J. Chem. Soc., Perkin Trans. 1 (1994), 1187, ibid.1
(1996), 2345; WO-A 99/41255; Aust. J. Chem. vol. 43 (1990), 733; J.
Org. Chem. vol. 43 (1978), 358; J. Chem. Soc., Chem. Commun.
(1979), 866; Tetrahedron Lett. vol. 34 (1993), 8267; ibid. vol. 33
(1992), 413.
The substituent R.sup.a in formula IA' can also be introduced as
shown in Scheme 4.
##STR00009##
Here, the compounds of the formula IA are initially converted with
the aid of strong bases into the anion and then reacted with the
corresponding acid chlorides to give IA' (see J. Chem. Soc., Perkin
Trans I, 1995, p. 3043). This gives compounds in which X is a
C.dbd.O bridge. Bases suitable for preparing the anion are, for
example, sodium amide and sodium hydride.
What was said above refers in particular to the preparation of
compounds in which R.sup.3 is an alkyl group. If R.sup.3 is a cyano
group or an alkoxy substituent, the radical R.sup.3 can be
introduced by reaction with alkali metal cyanides and alkali metal
alkoxides, respectively.
In the definitions of the symbols given in the formulae above,
collective terms were used which are generally representative for
the following substituents: halogen: fluorine, chlorine, bromine
and iodine; alkyl and the alkyl moieties of, for example, alkoxy,
alkylamino, alkoxycarbonyl: saturated straight-chain or branched
hydrocarbon radicals having 1 to 4, 6 or 8 carbon atoms, for
example C.sub.1-C.sub.6-alkyl such as methyl, ethyl, propyl,
1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl,
1,1-dimethylethyl, pentyl, 1-methylbutyl, 2-methylbutyl,
3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, hexyl,
1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl,
2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl,
1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl,
2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl,
1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl,
1-ethyl-1-methylpropyl and 1-ethyl-2-methylpropyl; haloalkyl:
straight-chain or branched alkyl groups having 1 to 8 carbon atoms
(as mentioned above), where in these groups some or all of the
hydrogen atoms may be replaced by halogen atoms as mentioned above,
for example C.sub.1-C.sub.2-haloalkyl, such as chloromethyl,
bromomethyl, dichloromethyl, trichloromethyl, fluoromethyl,
difluoromethyl, trifluoromethyl, chlorofluoromethyl,
dichlorofluoromethyl, chlorodifluoromethyl, 1-chloroethyl,
1-bromoethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl,
2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl,
2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl,
2,2,2-trichloroethyl, pentafluoroethyl or 1,1,1-trifluoroprop-2-yl;
alkenyl: unsaturated straight-chain or branched hydrocarbon
radicals having 2 to 4, 6 or 8 carbon atoms and a double bond in
any position, for example C.sub.2-C.sub.6-alkenyl, such as ethenyl,
1-propenyl, 2-propenyl, 1-methylethenyl, 1-butenyl, 2-butenyl,
3-butenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl,
1-methyl-2-propenyl, 2-methyl-2-propenyl, 1-pentenyl, 2-pentenyl,
3-pentenyl, 4-pentenyl, 1-methyl-1-butenyl, 2-methyl-1-butenyl,
3-methyl-1-butenyl, 1-methyl-2-butenyl, 2-methyl-2-butenyl,
3-methyl-2-butenyl, 1-methyl-3-butenyl, 2-methyl-3-butenyl,
3-methyl-3-butenyl, 1,1-dimethyl-2-propenyl,
1,2-dimethyl-1-propenyl, 1,2-dimethyl-2-propenyl,
1-ethyl-1-propenyl, 1-ethyl-2-propenyl, 1-hexenyl, 2-hexenyl,
3-hexenyl, 4-hexenyl, 5-hexenyl, 1-methyl-1-pentenyl,
2-methyl-1-pentenyl, 3-methyl-1-pentenyl, 4-methyl-1-pentenyl,
1-methyl-2-pentenyl, 2-methyl-2-pentenyl, 3-methyl-2-pentenyl,
4-methyl-2-pentenyl, 1-methyl-3-pentenyl, 2-methyl-3-pentenyl,
3-methyl-3-pentenyl, 4-methyl-3-pentenyl, 1-methyl-4-pentenyl,
2-methyl-4-pentenyl, 3-methyl-4-pentenyl, 4-methyl-4-pentenyl,
1,1-dimethyl-2-butenyl, 1,1-dimethyl-3-butenyl,
1,2-dimethyl-1-butenyl, 1,2-dimethyl-2-butenyl,
1,2-dimethyl-3-butenyl, 1,3-dimethyl-1-butenyl,
1,3-dimethyl-2-butenyl, 1,3-dimethyl-3-butenyl,
2,2-dimethyl-3-butenyl, 2,3-dimethyl-1-butenyl,
2,3-dimethyl-2-butenyl, 2,3-dimethyl-3-butenyl,
3,3-dimethyl-1-butenyl, 3,3-dimethyl-2-butenyl, 1-ethyl-1-butenyl,
1-ethyl-2-butenyl, 1-ethyl-3-butenyl, 2-ethyl-1-butenyl,
2-ethyl-2-butenyl, 2-ethyl-3-butenyl, 1,1,2-trimethyl-2-propenyl,
1-ethyl-1-methyl-2-propenyl, 1-ethyl-2-methyl-1-propenyl and
1-ethyl-2-methyl-2-propenyl; alkadienyl: unsaturated straight-chain
or branched hydrocarbon radicals having 4 or 6 carbon atoms and two
double bonds in any position; haloalkenyl: unsaturated
straight-chain or branched hydrocarbon radicals having 2 to 6
carbon atoms and a double bond in any position (as mentioned
above), where in these groups some or all of the hydrogen atoms may
be replaced by halogen atoms as mentioned above, in particular by
fluorine, chlorine and bromine; alkynyl: straight-chain or branched
hydrocarbon groups having 2 to 8 carbon atoms and a triple bond in
any position, for example C.sub.2-C.sub.6-alkynyl, such as ethynyl,
1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl,
1-methyl-2-propynyl, 1-pentynyl, 2-pentynyl, 3-pentynyl,
4-pentynyl, 1-methyl-2-butynyl, 1-methyl-3-butynyl,
2-methyl-3-butynyl, 3-methyl-1-butynyl, 1,1-dimethyl-2-propynyl,
1-ethyl-2-propynyl, 1-hexynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl,
5-hexynyl, 1-methyl-2-pentynyl, 1-methyl-3-pentynyl,
1-methyl-4-pentynyl, 2-methyl-3-pentynyl, 2-methyl-4-pentynyl,
3-methyl-1-pentynyl, 3-methyl-4-pentynyl, 4-methyl-1-pentynyl,
4-methyl-2-pentynyl, 1,1-dimethyl-2-butynyl,
1,1-dimethyl-3-butynyl, 1,2-dimethyl-3-butynyl,
2,2-dimethyl-3-butynyl, 3,3-dimethyl-1-butynyl, 1-ethyl-2-butynyl,
1-ethyl-3-butynyl, 2-ethyl-3-butynyl and
1-ethyl-1-methyl-2-propynyl; cycloalkyl: mono- or bicyclic
saturated hydrocarbon groups having 3 to 6 carbon ring members, for
example C.sub.3-C.sub.6-cycloalkyl such as cyclopropyl, cyclobutyl,
cyclopentyl, cyclohexyl;
five- or six-membered saturated, partially unsaturated or aromatic
heterocycle which contains one to four heteroatoms from the group
consisting of O, N and S: 5- or 6-membered heterocyclyl which
contains one to three nitrogen atoms and/or one oxygen or sulfur
atom or one or two oxygen and/or sulfur atoms, for example
2-tetrahydrofuranyl, 3-tetrahydrofuranyl, 2-tetrahydrothienyl,
3-tetrahydrothienyl, 2-pyrrolidinyl, 3-pyrrolidinyl,
3-isoxazolidinyl, 4-isoxazolidinyl, 5-isoxazolidinyl,
3-isothiazolidinyl, 4-isothiazolidinyl, 5-isothiazolidinyl,
3-pyrazolidinyl, 4-pyrazolidinyl, 5-pyrazolidinyl, 2-oxazolidinyl,
4-oxazolidinyl, 5-oxazolidinyl, 2-thiazolidinyl, 4-thiazolidinyl,
5-thiazolidinyl, 2-imidazolidinyl, 4-imidazolidinyl,
1,2,4-oxadiazolidin-3-yl, 1,2,4-oxadiazolidin-5-yl,
1,2,4-thiadiazolidin-3-yl, 1,2,4-thiadiazolidin-5-yl,
1,2,4-triazolidin-3-yl, 1,3,4-oxadiazolidin-2-yl,
1,3,4-thiadiazolidin-2-yl, 1,3,4-triazolidin-2-yl,
2,3-dihydrofur-2-yl, 2,3-dihydrofur-3-yl, 2,4-dihydrofur-2-yl,
2,4-dihydrofur-3-yl, 2,3-dihydrothien-2-yl, 2,3-dihydrothien-3-yl,
2,4-dihydrothien-2-yl, 2,4-dihydrothien-3-yl, 2-pyrrolin-2-yl,
2-pyrrolin-3-yl, 3-pyrrolin-2-yl, 3-pyrrolin-3-yl,
2-isoxazolin-3-yl, 3-isoxazolin-3-yl, 4-isoxazolin-3-yl,
2-isoxazolin-4-yl, 3-isoxazolin-4-yl, 4-isoxazolin-4-yl,
2-isoxazolin-5-yl, 3-isoxazolin-5-yl, 4-isoxazolin-5-yl,
2-isothiazolin-3-yl, 3-isothiazolin-3-yl, 4-isothiazolin-3-yl,
2-isothiazolin-4-yl, 3-isothiazolin-4-yl, 4-isothiazolin-4-yl,
2-isothiazolin-5-yl, 3-isothiazolin-5-yl, 4-isothiazolin-5-yl,
2,3-dihydropyrazol-1-yl, 2,3-dihydropyrazol-2-yl,
2,3-dihydropyrazol-3-yl, 2,3-dihydropyrazol-4-yl,
2,3-dihydropyrazol-5-yl, 3,4-dihydropyrazol-1-yl,
3,4-dihydropyrazol-3-yl, 3,4-dihydropyrazol-4-yl,
3,4-dihydropyrazol-5-yl, 4,5-dihydropyrazol-1-yl,
4,5-dihydropyrazol-3-yl, 4,5-dihydropyrazol-4-yl,
4,5-dihydropyrazol-5-yl, 2,3-dihydrooxazol-2-yl,
2,3-dihydrooxazol-3-yl, 2,3-dihydrooxazol-4-yl,
2,3-dihydrooxazol-5-yl, 3,4-dihydrooxazol-2-yl,
3,4-dihydrooxazol-3-yl, 3,4-dihydrooxazol-4-yl,
3,4-dihydrooxazol-5-yl, 3,4-dihydrooxazol-2-yl,
3,4-dihydrooxazol-3-yl, 3,4-dihydrooxazol-4-yl, 2-piperidinyl,
3-piperidinyl, 4-piperidinyl, 1,3-dioxan-5-yl, 2-tetrahydropyranyl,
4-tetrahydropyranyl, 2-tetrahydrothienyl, 3-hexahydropyridazinyl,
4-hexahydropyridazinyl, 2-hexahydropyrimidinyl,
4-hexahydropyrimidinyl, 5-hexahydropyrimidinyl, 2-piperazinyl,
1,3,5-hexahydrotriazin-2-yl and 1,2,4-hexahydrotriazin-3-yl;
5-membered heteroaryl which contains one to four nitrogen atoms or
one to three nitrogen atoms and one sulfur or oxygen atom:
5-membered heteroaryl groups which, in addition to carbon atoms,
may contain one to four nitrogen atoms or one to three nitrogen
atoms and one sulfur or oxygen atom as ring members, for example
2-furyl, 3-furyl, 2-thienyl, 3-thienyl, 2-pyrrolyl, 3-pyrrolyl,
3-isoxazolyl, 4-isoxazolyl, 5-isoxazolyl, 3-isothiazolyl,
4-isothiazolyl, 5-isothiazolyl, 3-pyrazolyl, 4-pyrazolyl,
5-pyrazolyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, 2-thiazolyl,
4-thiazolyl, 5-thiazolyl, 2-imidazolyl, 4-imidazolyl,
1,2,4-oxadiazol-3-yl, 1,2,4-oxadiazol-5-yl, 1,2,4-thiadiazol-3-yl,
1,2,4-thiadiazol-5-yl, 1,2,4-triazol-3-yl, 1,3,4-oxadiazol-2-yl,
1,3,4-thiadiazol-2-yl and 1,3,4-triazol-2-yl; 6-membered heteroaryl
which contains one to three or one to four nitrogen atoms:
6-membered heteroaryl groups which, in addition to carbon atoms,
may contain one to three and one to four nitrogen atoms,
respectively, as ring members, for example 2-pyridinyl,
3-pyridinyl, 4-pyridinyl, 3-pyridazinyl, 4-pyridazinyl,
2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl, 2-pyrazinyl,
1,3,5-triazin-2-yl and 1,2,4-triazin-3-yl; a ring system which, if
appropriate, is formed by R.sup.1 und R.sup.2 or by A and A'
together with the nitrogen to which they are attached: pyrrolidine,
morpholine, piperidine or tetrahydropyrazole.
The scope of the present invention includes the (R) and (S) isomers
and the racemates of compounds of the formula I having chiral
centers.
Hereinbelow, the embodiments of the invention are described in more
detail.
With a view to the intended use of the pyrimidines of the formula
I, particular preference is given to the following meanings of the
substituents, in each case on their own or in combination:
Preference is given to compounds I in which R.sup.1 is
C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-haloalkyl,
C.sub.2-C.sub.6-alkenyl, C.sub.2-C.sub.6-alkynyl or
C.sub.3-C.sub.6-cycloalkyl and R.sup.2 is hydrogen.
Especially preferred are compounds I in which R.sup.1 is
C.sub.1-C.sub.6-alkyl, C.sub.2-C.sub.6-alkenyl or
C.sub.1-C.sub.6-haloalkyl branched in the .alpha.-position.
In addition, preference is given to compounds I in which R.sup.1 is
C.sub.1-C.sub.4-haloalkyl and R.sup.2 is hydrogen.
Moreover, preference is given to compounds I in which R.sup.1 and
R.sup.2 together with the nitrogen to which they are attached form
a five- or six-membered ring which may be interrupted by an oxygen
atom and may carry one or two C.sub.1-C.sub.6-alkyl
substituents.
Especially preferred are groups NR.sup.1R.sup.2 such as--in
particular in the .alpha.-position--methylated pyrrolidines or
piperidines. Preference is furthermore given to
4-methylpiperidine.
Especially preferred are pyrimidines I in which the substituents
L.sup.1 to L.sup.5 are as defined below: L is halogen, cyano,
C.sub.1-C.sub.8-alkyl, C.sub.1-C.sub.6-alkoxy, --C(.dbd.O)--O-A,
--C(.dbd.O)--N(A')A, A, A', A'' independently of one another are
hydrogen, C.sub.1-C.sub.6-alkyl, C.sub.2-C.sub.6-alkenyl,
C.sub.2-C.sub.6-alkynyl.
Moreover, preference is given to pyrimidines I where the phenyl
group substituted by L.sub.n is the group B
##STR00010## where # is the point of attachment to the pyrimidine
skeleton and L.sup.1 is fluorine, chlorine, CH.sub.3 or CF.sub.3;
L.sup.2,L.sup.4 independently of one another are hydrogen, CH.sub.3
or fluorine; L.sup.3 is hydrogen, fluorine, chlorine, bromine,
cyano, CH.sub.3, SCH.sub.3, OCH.sub.3, SO.sub.2CH.sub.3,
CO--NH.sub.2, CO--NHCH.sub.3, CO--NHC.sub.2H.sub.5,
CO--N(CH.sub.3).sub.2, NH--C(.dbd.O)CH.sub.3,
N(CH.sub.3)--C(.dbd.O)CH.sub.3 or COOCH.sub.3 and L.sup.5 is
hydrogen, fluorine, chlorine or CH.sub.3.
Particular preference is also given to compounds I in which R.sup.3
is C.sub.1-C.sub.4-alkyl which may be substituted by halogen.
Moreover, particular preference is given to compounds I in which
R.sup.3 is halogen, cyano, C.sub.1-C.sub.4-alkyl or
C.sub.1-C.sub.4-alkoxy.
Especially preferred are compounds I in which R.sup.3 is methyl,
cyano, methoxy or in particular chlorine.
Suitable with a view to their fungicidal action are pyrimidines of
the formula I in which R.sup.4 is
##STR00011##
Preference is furthermore given to pyrimidines of the formula I in
which R.sup.4 is
##STR00012##
Especially preferred are pyrimidines of the formula I in which
R.sup.4 is
##STR00013##
Finally, R.sup.4 may preferably have the following meanings which
may also be interpreted as definitions of prodrug radicals (see
Medicinal Research Reviews 2003, 23, 763-793, or J. of
Pharmaceutical Sciences 1997, 86, 765-767):
##STR00014##
The index n in the alkenylene radicals of the above formulae is an
integer from 1 to 3. Especially preferred are the following radical
definitions R.sup.4:
##STR00015##
The bridge X is preferably a direct bond or --(C.dbd.O)--.
The substituent R.sup.a is preferably hydrogen, methyl, benzyl,
trifluoromethyl, allyl, propargyl or methoxymethyl and particularly
preferably hydrogen.
The substituent R.sup.b is preferably hydrogen,
C.sub.1-C.sub.6-alkyl or C.sub.2-C.sub.6-alkenyl and particularly
preferably: methyl, allyl or propargyl.
The substituent R.sup.c is preferably hydrogen or methyl.
The esters of the formula V
##STR00016## are both interesting intermediates and excellent
fungicidally active compounds.
The preferences in the definitions of L.sub.n and R.sup.1 to
R.sup.3 mentioned above apply correspondingly to the esters of the
formula V.
R' is in particular a C.sub.1-C.sub.6-alkyl radical, especially
preferably an isopropyl radical.
However, R' may also have the meanings allyl, propargyl, benzyl,
aminoalkyl, hydroxyalkyl, alkoxyalkyl or haloalkyl.
In particular with a view to their use, preference is given to
compounds I and V compiled in the tables below. Moreover, the
groups mentioned for a substituent in the tables are per se,
independently of the combination in which they are mentioned, a
particularly preferred embodiment of the substituent in
question.
##STR00017## ##STR00018## Table 1
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2-fluoro-6-chloro, R.sup.3 is methyl and
R.sup.1, R.sup.2 for a compound correspond in each case to one row
of Table A
Table 2
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2,6-difluoro, R.sup.3 is methyl and R.sup.1,
R.sup.2 for a compound correspond in each case to one row of Table
A
Table 3
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2,6-dichloro, R.sup.3 is methyl and R.sup.1,
R.sup.2 for a compound correspond in each case to one row of Table
A
Table 4
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2-fluoro-6-methyl, R.sup.3 is methyl and
R.sup.1, R.sup.2 for a compound correspond in each case to one row
of Table A
Table 5
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2,4,6-trifluoro, R.sup.3 is methyl and R.sup.1,
R.sup.2 for a compound correspond in each case to one row of Table
A
Table 6
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2-methyl-4-fluoro, R.sup.3 is methyl and
R.sup.1, R.sup.2 for a compound correspond in each case to one row
of Table A
Table 7
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2-fluoro-4-methoxycarbonyl, R.sup.3 is methyl
and R.sup.1, R.sup.2 for a compound correspond in each case to one
row of Table A
Table 8
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2-fluoro-4-CN, R.sup.3 is methyl and R.sup.1,
R.sup.2 for a compound correspond in each case to one row of Table
A
Table 9
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2,4,5-trifluoro, R.sup.3 is methyl and R.sup.1,
R.sup.2 for a compound correspond in each case to one row of Table
A
Table 10
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2,4-dichloro, R.sup.3 is methyl and R.sup.1,
R.sup.2 for a compound correspond in each case to one row of Table
A
Table 11
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2-chloro, R.sup.3 is methyl and R.sup.1,
R.sup.2 for a compound correspond in each case to one row of Table
A
Table 12
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2-fluoro, R.sup.3 is methyl and R.sup.1,
R.sup.2 for a compound correspond in each case to one row of Table
A
Table 13
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2,4-difluoro, R.sup.3 is methyl and R.sup.1,
R.sup.2 for a compound correspond in each case to one row of Table
A
Table 14
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2-fluoro-4-chloro, R.sup.3 is methyl and
R.sup.1, R.sup.2 for a compound correspond in each case to one row
of Table A
Table 15
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2-chloro-4-fluoro, R.sup.3 is methyl and
R.sup.1, R.sup.2 for a compound correspond in each case to one row
of Table A
Table 16
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2,3-difluoro, R.sup.3 is methyl and R.sup.1,
R.sup.2 for a compound correspond in each case to one row of Table
A
Table 17
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2,5-difluoro, R.sup.3 is methyl and R.sup.1,
R.sup.2 for a compound correspond in each case to one row of Table
A
Table 18
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2,3,4-trifluoro, R.sup.3 is methyl and R.sup.1,
R.sup.2 for a compound correspond in each case to one row of Table
A
Table 19
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2-methyl, R.sup.3 is methyl and R.sup.1,
R.sup.2 for a compound correspond in each case to one row of Table
A
Table 20
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2,4-dimethyl, R.sup.3 is methyl and R.sup.1,
R.sup.2 for a compound correspond in each case to one row of Table
A
Table 21
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2-methyl-4-chloro, R.sup.3 is methyl and
R.sup.1, R.sup.2 for a compound correspond in each case to one row
of Table A
Table 22
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2-fluoro-4-methyl, R.sup.3 is methyl and
R.sup.1, R.sup.2 for a compound correspond in each case to one row
of Table A
Table 23
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2,6-dimethyl, R.sup.3 is methyl and R.sup.1,
R.sup.2 for a compound correspond in each case to one row of Table
A
Table 24
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2,4,6-trimethyl, R.sup.3 is methyl and R.sup.1,
R.sup.2 for a compound correspond in each case to one row of Table
A
Table 25
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2,6-difluoro-4-cyano, R.sup.3 is methyl and
R.sup.1, R.sup.2 for a compound correspond in each case to one row
of Table A
Table 26
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2,6-difluoro-4-methyl, R.sup.3 is methyl and
R.sup.1, R.sup.2 for a compound correspond in each case to one row
of Table A
Table 27
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2,6-difluoro-4-methoxycarbonyl, R.sup.3 is
methyl and R.sup.1, R.sup.2 for a compound correspond in each case
to one row of Table A
Table 28
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2-chloro, 4-methoxy, R.sup.3 is methyl and
R.sup.1, R.sup.2 for a compound correspond in each case to one row
of Table A
Table 29
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2-chloro, 4-methyl, R.sup.3 is methyl and
R.sup.1, R.sup.2 for a compound correspond in each case to one row
of Table A
Table 30
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2-chloro, 4-methoxycarbonyl, R.sup.3 is methyl
and R.sup.1, R.sup.2 for a compound correspond in each case to one
row of Table A
Table 31
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2-chloro, 4-bromo, R.sup.3 is methyl and
R.sup.1, R.sup.2 for a compound correspond in each case to one row
of Table A
Table 32
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2-chloro, 4-cyano, R.sup.3 is methyl and
R.sup.1, R.sup.2 for a compound correspond in each case to one row
of Table A
Table 33
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2,6-difluoro, 4-methoxy, R.sup.3 is methyl and
R.sup.1, R.sup.2 for a compound correspond in each case to one row
of Table A
Table 34
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2-fluoro, 3-methyl, R.sup.3 is methyl and
R.sup.1, R.sup.2 for a compound correspond in each case to one row
of Table A
Table 35
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2,5-dimethyl, R.sup.3 is methyl and R.sup.1,
R.sup.2 for a compound correspond in each case to one row of Table
A
Table 36
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2-methyl, 4-cyano, R.sup.3 is methyl and
R.sup.1, R.sup.2 for a compound correspond in each case to one row
of Table A
Table 37
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2-methyl, 4-bromo, R.sup.3 is methyl and
R.sup.1, R.sup.2 for a compound correspond in each case to one row
of Table A
Table 38
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2-methyl, 5-fluoro, R.sup.3 is methyl and
R.sup.1, R.sup.2 for a compound correspond in each case to one row
of Table A
Table 39
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2-methyl, 4-methoxy, R.sup.3 is methyl and
R.sup.1, R.sup.2 for a compound correspond in each case to one row
of Table A
Table 40
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2-methyl, 4-methoxycarbonyl, R.sup.3 is methyl
and R.sup.1, R.sup.2 for a compound correspond in each case to one
row of Table A
Table 41
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2,5-dimethyl, 4-bromo, R.sup.3 is methyl and
R.sup.1, R.sup.2 for a compound correspond in each case to one row
of Table A
Table 42
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2-fluoro, 4-bromo, R.sup.3 is methyl and
R.sup.1, R.sup.2 for a compound correspond in each case to one row
of Table A
Table 43
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2-fluoro, 4-methoxy, R.sup.3 is methyl and
R.sup.1, R.sup.2 for a compound correspond in each case to one row
of Table A
Table 44
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2-fluoro, 5-methyl, R.sup.3 is methyl and
R.sup.1, R.sup.2 for a compound correspond in each case to one row
of Table A
Table 45
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is pentafluoro, R.sup.3 is methyl and R.sup.1,
R.sup.2 for a compound correspond in each case to one row of Table
A
Table 46
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2-fluoro, 6-chloro, R.sup.3 is chloro and
R.sup.1, R.sup.2 for a compound correspond in each case to one row
of Table A
Table 47
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2,6-difluoro, R.sup.3 is chloro and R.sup.1,
R.sup.2 for a compound correspond in each case to one row of Table
A
Table 48
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2,6-dichloro, R.sup.3 is chloro and R.sup.1,
R.sup.2 for a compound correspond in each case to one row of Table
A
Table 49
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2-fluoro, 6-methyl, R.sup.3 is chloro and
R.sup.1, R.sup.2 for a compound correspond in each case to one row
of Table A
Table 50
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2,4,6-trifluoro, R.sup.3 is chloro and R.sup.1,
R.sup.2 for a compound correspond in each case to one row of Table
A
Table 51
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2-methyl, 4-fluoro, R.sup.3 is chloro and
R.sup.1, R.sup.2 for a compound correspond in each case to one row
of Table A
Table 52
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2-fluoro, 4-methoxycarbonyl, R.sup.3 is chloro
and R.sup.1, R.sup.2 for a compound correspond in each case to one
row of Table A
Table 53
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2-fluoro, 4-CN, R.sup.3 is chloro and R.sup.1,
R.sup.2 for a compound correspond in each case to one row of Table
A
Table 54
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2,4,5-trifluoro, R.sup.3 is chloro and R.sup.1,
R.sup.2 for a compound correspond in each case to one row of Table
A
Table 55
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2,4-dichloro, R.sup.3 is chloro and R.sup.1,
R.sup.2 for a compound correspond in each case to one row of Table
A
56
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2-chloro, R.sup.3 is chloro and R.sup.1,
R.sup.2 for a compound correspond in each case to one row of Table
A
Table 57
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2-fluoro, R.sup.3 is chloro and R.sup.1,
R.sup.2 for a compound correspond in each case to one row of Table
A
Table 58
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2,4-difluoro, R.sup.3 is chloro and R.sup.1,
R.sup.2 for a compound correspond in each case to one row of Table
A
Table 59
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2-fluoro-4-chloro, R.sup.3 is chloro and
R.sup.1, R.sup.2 for a compound correspond in each case to one row
of Table A
Table 60
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2-chloro-4-fluoro, R.sup.3 is chloro and
R.sup.1, R.sup.2 for a compound correspond in each case to one row
of Table A
Table 61
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2,3-difluoro, R.sup.3 is chloro and R.sup.1,
R.sup.2 for a compound correspond in each case to one row of Table
A
Table 62
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2,5-difluoro, R.sup.3 is chloro and R.sup.1,
R.sup.2 for a compound correspond in each case to one row of Table
A
Table 63
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2,3,4-trifluoro, R.sup.3 is chloro and R.sup.1,
R.sup.2 for a compound correspond in each case to one row of Table
A
Table 64
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2-methyl, R.sup.3 is chloro and R.sup.1,
R.sup.2 for a compound correspond in each case to one row of Table
A
Table 65
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2,4-dimethyl, R.sup.3 is chloro and R.sup.1,
R.sup.2 for a compound correspond in each case to one row of Table
A
Table 66
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2-methyl-4-chloro, R.sup.3 is chloro and
R.sup.1, R.sup.2 for a compound correspond in each case to one row
of Table A
Table 67
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2-fluoro-4-methyl, R.sup.3 is chloro and
R.sup.1, R.sup.2 for a compound correspond in each case to one row
of Table A
Table 68
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2,6-dimethyl, R.sup.3 is chloro and R.sup.1,
R.sup.2 for a compound correspond in each case to one row of Table
A
Table 69
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2,4,6-trimethyl, R.sup.3 is chloro and R.sup.1,
R.sup.2 for a compound correspond in each case to one row of Table
A
Table 70
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2,6-difluoro-4-cyano, R.sup.3 is chloro and
R.sup.1, R.sup.2 for a compound correspond in each case to one row
of Table A
Table 71
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2,6-difluoro-4-methyl, R.sup.3 is chloro and
R.sup.1, R.sup.2 for a compound correspond in each case to one row
of Table A
Table 72
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2,6-difluoro-4-methoxycarbonyl, R.sup.3 is
chloro and R.sup.1, R.sup.2 for a compound correspond in each case
to one row of Table A
Table 73
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2-chloro, 4-methoxy, R.sup.3 is chloro and
R.sup.1, R.sup.2 for a compound correspond in each case to one row
of Table A
Table 74
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2-chloro, 4-methyl, R.sup.3 is chloro and
R.sup.1, R.sup.2 for a compound correspond in each case to one row
of Table A
Table 75
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2-chloro, 4-methoxycarbonyl, R.sup.3 is chloro
and R.sup.1, R.sup.2 for a compound correspond in each case to one
row of Table A
Table 76
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2-chloro, 4-bromo, R.sup.3 is chloro and
R.sup.1, R.sup.2 for a compound correspond in each case to one row
of Table A
Table 77
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2-chloro, 4-cyano, R.sup.3 is chloro and
R.sup.1, R.sup.2 for a compound correspond in each case to one row
of Table A
Table 78
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2,6-difluoro, 4-methoxy, R.sup.3 is chloro and
R.sup.1, R.sup.2 for a compound correspond in each case to one row
of Table A
Table 79
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2-fluoro, 3-methyl, R.sup.3 is chloro and
R.sup.1, R.sup.2 for a compound correspond in each case to one row
of Table A
Table 80
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2,5-dimethyl, R.sup.3 is chloro and R.sup.1,
R.sup.2 for a compound correspond in each case to one row of Table
A
Table 81
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2-methyl, 4-cyano, R.sup.3 is chloro and
R.sup.1, R.sup.2 for a compound correspond in each case to one row
of Table A
Table 82
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2-methyl, 4-bromo, R.sup.3 is chloro and
R.sup.1, R.sup.2 for a compound correspond in each case to one row
of Table A
Table 83
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2-methyl, 5-fluoro, R.sup.3 is chloro and
R.sup.1, R.sup.2 for a compound correspond in each case to one row
of Table A
Table 84
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2-methyl, 4-methoxy, R.sup.3 is chloro and
R.sup.1, R.sup.2 for a compound correspond in each case to one row
of Table A
Table 85
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2-methyl, 4-methoxycarbonyl, R.sup.3 is chloro
and R.sup.1, R.sup.2 for a compound correspond in each case to one
row of Table A
Table 86
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2,5-dimethyl, 4-bromo, R.sup.3 is chloro and
R.sup.1, R.sup.2 for a compound correspond in each case to one row
of Table A
Table 87
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2-fluoro, 4-bromo, R.sup.3 is chloro and
R.sup.1, R.sup.2 for a compound correspond in each case to one row
of Table A
Table 88
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2-fluoro, 4-methoxy, R.sup.3 is chloro and
R.sup.1, R.sup.2 for a compound correspond in each case to one row
of Table A
Table 89
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2-fluoro, 5-methyl, R.sup.3 is chloro and
R.sup.1, R.sup.2 for a compound correspond in each case to one row
of Table A
Table 90
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is pentafluoro, R.sup.3 is chloro and R.sup.1,
R.sup.2 for a compound correspond in each case to one row of Table
A
Table 91
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2-fluoro, 6-chloro, R.sup.3 is methoxy and
R.sup.1, R.sup.2 for a compound correspond in each case to one row
of Table A
Table 92
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2,6-difluoro, R.sup.3 is methoxy and R.sup.1,
R.sup.2 for a compound correspond in each case to one row of Table
A
Table 93
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2,6-dichloro, R.sup.3 is methoxy and R.sup.1,
R.sup.2 for a compound correspond in each case to one row of Table
A
Table 94
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2-fluoro, 6-methyl, R.sup.3 is methoxy and
R.sup.1, R.sup.2 for a compound correspond in each case to one row
of Table A
Table 95
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2,4,6-trifluoro, R.sup.3 is methoxy and
R.sup.1, R.sup.2 for a compound correspond in each case to one row
of Table A
Table 96
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2-methyl, 4-fluoro, R.sup.3 is methoxy and
R.sup.1, R.sup.2 for a compound correspond in each case to one row
of Table A
Table 97
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2-fluoro, 4-methoxycarbonyl, R.sup.3 is methoxy
and R.sup.1, R.sup.2 for a compound correspond in each case to one
row of Table A
Table 98
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2-fluoro, 4-CN, R.sup.3 is methoxy and R.sup.1,
R.sup.2 for a compound correspond in each case to one row of Table
A
Table 99
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2,4,5-trifluoro, R.sup.3 is methoxy and
R.sup.1, R.sup.2 for a compound correspond in each case to one row
of Table A
Table 100
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2,4-dichloro, R.sup.3 is methoxy and R.sup.1,
R.sup.2 for a compound correspond in each case to one row of Table
A
Table 101
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2-chloro, R.sup.3 is methoxy and R.sup.1,
R.sup.2 for a compound correspond in each case to one row of Table
A
Table 102
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2-fluoro, R.sup.3 is methoxy and R.sup.1,
R.sup.2 for a compound correspond in each case to one row of Table
A
Table 103
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2,4-difluoro, R.sup.3 is methoxy and R.sup.1,
R.sup.2 for a compound correspond in each case to one row of Table
A
Table 104
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2-fluoro-4-chloro, R.sup.3 is methoxy and
R.sup.1, R.sup.2 for a compound correspond in each case to one row
of Table A
Table 105
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2-chloro-4-fluoro, R.sup.3 is methoxy and
R.sup.1, R.sup.2 for a compound correspond in each case to one row
of Table A
Table 106
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2,3-difluoro, R.sup.3 is methoxy and R.sup.1,
R.sup.2 for a compound correspond in each case to one row of Table
A
Table 107
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2,5-difluoro, R.sup.3 is methoxy and R.sup.1,
R.sup.2 for a compound correspond in each case to one row of Table
A
Table 108
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2,3,4-trifluoro, R.sup.3 is methoxy and
R.sup.1, R.sup.2 for a compound correspond in each case to one row
of Table A
Table 109
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2-methyl, R.sup.3 is methoxy and R.sup.1,
R.sup.2 for a compound correspond in each case to one row of Table
A
Table 110
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2,4-dimethyl, R.sup.3 is methoxy and R.sup.1,
R.sup.2 for a compound correspond in each case to one row of Table
A
Table 111
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2-methyl-4-chloro, R.sup.3 is methoxy and
R.sup.1, R.sup.2 for a compound correspond in each case to one row
of Table A
Table 112
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2-fluoro-4-methyl, R.sup.3 is methoxy and
R.sup.1, R.sup.2 for a compound correspond in each case to one row
of Table A
Table 113
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2,6-dimethyl, R.sup.3 is methoxy and R.sup.1,
R.sup.2 for a compound correspond in each case to one row of Table
A
Table 114
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2,4,6-trimethyl, R.sup.3 is methoxy and
R.sup.1, R.sup.2 for a compound correspond in each case to one row
of Table A
Table 115
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2,6-difluoro-4-cyano, R.sup.3 is methoxy and
R.sup.1, R.sup.2 for a compound correspond in each case to one row
of Table A
Table 116
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2,6-difluoro-4-methyl, R.sup.3 is methoxy and
R.sup.1, R.sup.2 for a compound correspond in each case to one row
of Table A
Table 117
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2,6-difluoro-4-methoxycarbonyl, R.sup.3 is
methoxy and R.sup.1, R.sup.2 for a compound correspond in each case
to one row of Table A
Table 118
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2-chloro, 4-methoxy, R.sup.3 is methoxy and
R.sup.1, R.sup.2 for a compound correspond in each case to one row
of Table A
Table 119
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2-chloro, 4-methyl, R.sup.3 is methoxy and
R.sup.1, R.sup.2 for a compound correspond in each case to one row
of Table A
Table 120
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2-chloro, 4-methoxycarbonyl, R.sup.3 is methoxy
and R.sup.1, R.sup.2 for a compound correspond in each case to one
row of Table A
Table 121
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2-chloro, 4-methoxy, R.sup.3 is methoxy and
R.sup.1, R.sup.2 for a compound correspond in each case to one row
of Table A
Table 122
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2-chloro, 4-cyano, R.sup.3 is methoxy and
R.sup.1, R.sup.2 for a compound correspond in each case to one row
of Table A
Table 123
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2,6-difluoro, 4-methoxy, R.sup.3 is methoxy and
R.sup.1, R.sup.2 for a compound correspond in each case to one row
of Table A
Table 124
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2-fluoro, 3-methyl, R.sup.3 is methoxy and
R.sup.1, R.sup.2 for a compound correspond in each case to one row
of Table A
Table 125
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2,5-dimethyl, R.sup.3 is methoxy and R.sup.1,
R.sup.2 for a compound correspond in each case to one row of Table
A
Table 126
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2-methyl, 4-cyano, R.sup.3 is methoxy and
R.sup.1, R.sup.2 for a compound correspond in each case to one row
of Table A
Table 127
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2-methyl, 4-bromo, R.sup.3 is methoxy and
R.sup.1, R.sup.2 for a compound correspond in each case to one row
of Table A
Table 128
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2-methyl, 5-fluoro, R.sup.3 is methoxy and
R.sup.1, R.sup.2 for a compound correspond in each case to one row
of Table A
Table 129
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2-methyl, 4-methoxy, R.sup.3 is methoxy and
R.sup.1, R.sup.2 for a compound correspond in each case to one row
of Table A
Table 130
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2-methyl, 4-methoxycarbonyl, R.sup.3 is methoxy
and R.sup.1, R.sup.2 for a compound correspond in each case to one
row of Table A
Table 131
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2,5-dimethyl, 4-bromo, R.sup.3 is methoxy and
R.sup.1, R.sup.2 for a compound correspond in each case to one row
of Table A
Table 132
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2-fluoro, 4-bromo, R.sup.3 is methoxy and
R.sup.1, R.sup.2 for a compound correspond in each case to one row
of Table A
Table 133
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2-fluoro, 4-methoxy, R.sup.3 is methoxy and
R.sup.1, R.sup.2 for a compound correspond in each case to one row
of Table A
Table 134
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2-fluoro, 5-methyl, R.sup.3 is methoxy and
R.sup.1, R.sup.2 for a compound correspond in each case to one row
of Table A
Table 135
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is pentafluoro, R.sup.3 is methoxy and R.sup.1,
R.sup.2 for a compound correspond in each case to one row of Table
A
Table 136
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2-fluoro, 6-chloro, R.sup.3 is cyano and
R.sup.1, R.sup.2 for a compound correspond in each case to one row
of Table A
Table 137
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2,6-difluoro, R.sup.3 is cyano and R.sup.1,
R.sup.2 for a compound correspond in each case to one row of Table
A
Table 138
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2,6-dichloro, R.sup.3 is cyano and R.sup.1,
R.sup.2 for a compound correspond in each case to one row of Table
A
Table 139
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2-fluoro, 6-methyl, R.sup.3 is cyano and
R.sup.1, R.sup.2 for a compound correspond in each case to one row
of Table A
Table 140
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2,4,6-trifluoro, R.sup.3 is cyano and R.sup.1,
R.sup.2 for a compound correspond in each case to one row of Table
A
Table 141
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2-methyl, 4-fluoro, R.sup.3 is cyano and
R.sup.1, R.sup.2 for a compound correspond in each case to one row
of Table A
Table 142
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2-fluoro, 4-methoxycarbonyl, R.sup.3 is cyano
and R.sup.1, R.sup.2 for a compound correspond in each case to one
row of Table A
Table 143
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2-fluoro, 4-CN, R.sup.3 is cyano and R.sup.1,
R.sup.2 for a compound correspond in each case to one row of Table
A
Table 144
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2,4,5-trifluoro, R.sup.3 is cyano and R.sup.1,
R.sup.2 for a compound correspond in each case to one row of Table
A
Table 145
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2,4-dichloro, R.sup.3 is cyano and R.sup.1,
R.sup.2 for a compound correspond in each case to one row of Table
A
Table 146
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2-chloro, R.sup.3 is cyano and R.sup.1, R.sup.2
for a compound correspond in each case to one row of Table A
Table 147
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2-fluoro, R.sup.3 is cyano and R.sup.1, R.sup.2
for a compound correspond in each case to one row of Table A
Table 148
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2,4-difluoro, R.sup.3 is cyano and R.sup.1,
R.sup.2 for a compound correspond in each case to one row of Table
A
Table 149
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2-fluoro-4-chloro, R.sup.3 is cyano and
R.sup.1, R.sup.2 for a compound correspond in each case to one row
of Table A
Table 150
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2-chloro-4-fluoro, R.sup.3 is cyano and
R.sup.1, R.sup.2 for a compound correspond in each case to one row
of Table A
Table 151
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2,3-difluoro, R.sup.3 is cyano and R.sup.1,
R.sup.2 for a compound correspond in each case to one row of Table
A
Table 152
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2,5-difluoro, R.sup.3 is cyano and R.sup.1,
R.sup.2 for a compound correspond in each case to one row of Table
A
Table 153
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2,3,4-trifluoro, R.sup.3 is cyano and R.sup.1,
R.sup.2 for a compound correspond in each case to one row of Table
A
Table 154
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2-methyl, R.sup.3 is cyano and R.sup.1, R.sup.2
for a compound correspond in each case to one row of Table A
Table 155
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2,4-dimethyl, R.sup.3 is cyano and R.sup.1,
R.sup.2 for a compound correspond in each case to one row of Table
A
Table 156
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2-methyl-4-chloro, R.sup.3 is cyano and
R.sup.1, R.sup.2 for a compound correspond in each case to one row
of Table A
Table 157
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2-fluoro-4-methyl, R.sup.3 is cyano and
R.sup.1, R.sup.2 for a compound correspond in each case to one row
of Table A
Table 158
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2,6-dimethyl, R.sup.3 is cyano and R.sup.1,
R.sup.2 for a compound correspond in each case to one row of Table
A
Table 159
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2,4,6-trimethyl, R.sup.3 is cyano and R.sup.1,
R.sup.2 for a compound correspond in each case to one row of Table
A
Table 160
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2,6-difluoro-4-cyano, R.sup.3 is cyano and
R.sup.1, R.sup.2 for a compound correspond in each case to one row
of Table A
Table 161
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2,6-difluoro-4-methyl, R.sup.3 is cyano and
R.sup.1, R.sup.2 for a compound correspond in each case to one row
of Table A
Table 162
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2,6-difluoro-4-methoxycarbonyl, R.sup.3 is
cyano and R.sup.1, R.sup.2 for a compound correspond in each case
to one row of Table A
Table 163
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2-chloro, 4-methoxy, R.sup.3 is cyano and
R.sup.1, R.sup.2 for a compound correspond in each case to one row
of Table A
Table 164
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2-chloro, 4-methyl, R.sup.3 is cyano and
R.sup.1, R.sup.2 for a compound correspond in each case to one row
of Table A
Table 165
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2-chloro, 4-methoxycarbonyl, R.sup.3 is cyano
and R.sup.1, R.sup.2 for a compound correspond in each case to one
row of Table A
Table 166
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2-chloro, 4-bromo, R.sup.3 is cyano and
R.sup.1, R.sup.2 for a compound correspond in each case to one row
of Table A
Table 167
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2-chloro, 4-cyano, R.sup.3 is cyano and
R.sup.1, R.sup.2 for a compound correspond in each case to one row
of Table A
Table 168
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2,6-difluoro, 4-methoxy, R.sup.3 is cyano and
R.sup.1, R.sup.2 for a compound correspond in each case to one row
of Table A
Table 169
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2-fluoro, 3-methyl, R.sup.3 is cyano and
R.sup.1, R.sup.2 for a compound correspond in each case to one row
of Table A
Table 170
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2,5-dimethyl, R.sup.3 is cyano and R.sup.1,
R.sup.2 for a compound correspond in each case to one row of Table
A
Table 171
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2-methyl, 4-cyano, R.sup.3 is cyano and
R.sup.1, R.sup.2 for a compound correspond in each case to one row
of Table A
Table 172
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2-methyl, 4-bromo, R.sup.3 is cyano and
R.sup.1, R.sup.2 for a compound correspond in each case to one row
of Table A
Table 173
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2-methyl, 5-fluoro, R.sup.3 is cyano and
R.sup.1, R.sup.2 for a compound correspond in each case to one row
of Table A
Table 174
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2-methyl, 4-methoxy, R.sup.3 is cyano and
R.sup.1, R.sup.2 for a compound correspond in each case to one row
of Table A
Table 175
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2-methyl, 4-methoxycarbonyl, R.sup.3 is cyano
and R.sup.1, R.sup.2 for a compound correspond in each case to one
row of Table A
Table 176
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2,5-dimethyl, 4-bromo, R.sup.3 is cyano and
R.sup.1, R.sup.2 for a compound correspond in each case to one row
of Table A
Table 177
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2-fluoro, 4-bromo, R.sup.3 is cyano and
R.sup.1, R.sup.2 for a compound correspond in each case to one row
of Table A
Table 178
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2-fluoro, 4-methoxy, R.sup.3 is cyano and
R.sup.1, R.sup.2 for a compound correspond in each case to one row
of Table A
Table 179
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is 2-fluoro, 5-methyl, R.sup.3 is cyano and
R.sup.1, R.sup.2 for a compound correspond in each case to one row
of Table A
Table 180
Compounds of the formulae Ia, Ib, Ic, Id, Ie, If, Ig, Ih, Ii and Va
in which L.sub.n is pentafluoro, R.sup.3 is cyano and R.sup.1,
R.sup.2 for a compound correspond in each case to one row of Table
A
TABLE-US-00001 TABLE A No. R.sup.1 R.sup.2 A-1 CH.sub.2CH.sub.3 H
A-2 CH.sub.2CH.sub.3 CH.sub.3 A-3 CH.sub.2CH.sub.3 CH.sub.2CH.sub.3
A-4 CH.sub.2CH.sub.2CH.sub.3 H A-5 CH.sub.2CH.sub.2CH.sub.3
CH.sub.3 A-6 CH.sub.2CH.sub.2CH.sub.3 CH.sub.2CH.sub.3 A-7
CH.sub.2CH.sub.2CH.sub.3 CH.sub.2CH.sub.2CH.sub.3 A-8
CH.sub.2CH.sub.2F H A-9 CH.sub.2CH.sub.2F CH.sub.3 A-10
CH.sub.2CH.sub.2F CH.sub.2CH.sub.3 A-11 CH.sub.2CF.sub.3 H A-12
CH.sub.2CF.sub.3 CH.sub.3 A-13 CH.sub.2CF.sub.3 CH.sub.2CH.sub.3
A-14 CH.sub.2CF.sub.3 CH.sub.2CH.sub.2CH.sub.3 A-15
CH.sub.2CCl.sub.3 H A-16 CH.sub.2CCl.sub.3 CH.sub.3 A-17
CH.sub.2CCl.sub.3 CH.sub.2CH.sub.3 A-18 CH.sub.2CCl.sub.3
CH.sub.2CH.sub.2CH.sub.3 A-19 CH(CH.sub.3).sub.2 H A-20
CH(CH.sub.3).sub.2 CH.sub.3 A-21 CH(CH.sub.3).sub.2
CH.sub.2CH.sub.3 A-22 CH(CH.sub.3).sub.2 CH.sub.2CH.sub.2CH.sub.3
A-23 CH.sub.2C(CH.sub.3).sub.3 H A-24 CH.sub.2C(CH.sub.3).sub.3
CH.sub.3 A-25 CH.sub.2C(CH.sub.3).sub.3 CH.sub.2CH.sub.3 A-26
CH.sub.2CH(CH.sub.3).sub.2 H A-27 CH.sub.2CH(CH.sub.3).sub.2
CH.sub.3 A-28 CH.sub.2CH(CH.sub.3).sub.2 CH.sub.2CH.sub.3 A-29
(.+-.) CH(CH.sub.2CH.sub.3)CH.sub.3 H A-30 (.+-.)
CH(CH.sub.2CH.sub.3)CH.sub.3 CH.sub.3 A-31 (.+-.)
CH(CH.sub.2CH.sub.3)CH.sub.3 CH.sub.2CH.sub.3 A-32 (R)
CH(CH.sub.2CH.sub.3)CH.sub.3 H A-33 (R)
CH(CH.sub.2CH.sub.3)CH.sub.3 CH.sub.3 A-34 (R)
CH(CH.sub.2CH.sub.3)CH.sub.3 CH.sub.2CH.sub.3 A-35 (S)
CH(CH.sub.2CH.sub.3)CH.sub.3 H A-36 (S)
CH(CH.sub.2CH.sub.3)CH.sub.3 CH.sub.3 A-37 (S)
CH(CH.sub.2CH.sub.3)CH.sub.3 CH.sub.2CH.sub.3 A-38 (.+-.)
CH(CH.sub.3)--CH(CH.sub.3).sub.2 H A-39 (.+-.)
CH(CH.sub.3)--CH(CH.sub.3).sub.2 CH.sub.3 A-40 (.+-.)
CH(CH.sub.3)--CH(CH.sub.3).sub.2 CH.sub.2CH.sub.3 A-41 (R)
CH(CH.sub.3)--CH(CH.sub.3).sub.2 H A-42 (R)
CH(CH.sub.3)--CH(CH.sub.3).sub.2 CH.sub.3 A-43 (R)
CH(CH.sub.3)--CH(CH.sub.3).sub.2 CH.sub.2CH.sub.3 A-44 (S)
CH(CH.sub.3)--CH(CH.sub.3).sub.2 H A-45 (S)
CH(CH.sub.3)--CH(CH.sub.3).sub.2 CH.sub.3 A-46 (S)
CH(CH.sub.3)--CH(CH.sub.3).sub.2 CH.sub.2CH.sub.3 A-47 (.+-.)
CH(CH.sub.3)--C(CH.sub.3).sub.3 H A-48 (.+-.)
CH(CH.sub.3)--C(CH.sub.3).sub.3 CH.sub.3 A-49 (.+-.)
CH(CH.sub.3)--C(CH.sub.3).sub.3 CH.sub.2CH.sub.3 A-50 (R)
CH(CH.sub.3)--C(CH.sub.3).sub.3 H A-51 (R)
CH(CH.sub.3)--C(CH.sub.3).sub.3 CH.sub.3 A-52 (R)
CH(CH.sub.3)--C(CH.sub.3).sub.3 CH.sub.2CH.sub.3 A-53 (S)
CH(CH.sub.3)--C(CH.sub.3).sub.3 H A-54 (S)
CH(CH.sub.3)--C(CH.sub.3).sub.3 CH.sub.3 A-55 (S)
CH(CH.sub.3)--C(CH.sub.3).sub.3 CH.sub.2CH.sub.3 A-56 (.+-.)
CH(CH.sub.3)--CF.sub.3 H A-57 (.+-.) CH(CH.sub.3)--CF.sub.3
CH.sub.3 A-58 (.+-.) CH(CH.sub.3)--CF.sub.3 CH.sub.2CH.sub.3 A-59
(R) CH(CH.sub.3)--CF.sub.3 H A-60 (R) CH(CH.sub.3)--CF.sub.3
CH.sub.3 A-61 (R) CH(CH.sub.3)--CF.sub.3 CH.sub.2CH.sub.3 A-62 (S)
CH(CH.sub.3)--CF.sub.3 H A-63 (S) CH(CH.sub.3)--CF.sub.3 CH.sub.3
A-64 (S) CH(CH.sub.3)--CF.sub.3 CH.sub.2CH.sub.3 A-65 (.+-.)
CH(CH.sub.3)--CCl.sub.3 H A-66 (.+-.) CH(CH.sub.3)--CCl.sub.3
CH.sub.3 A-67 (.+-.) CH(CH.sub.3)--CCl.sub.3 CH.sub.2CH.sub.3 A-68
(R) CH(CH.sub.3)--CCl.sub.3 H A-69 (R) CH(CH.sub.3)--CCl.sub.3
CH.sub.3 A-70 (R) CH(CH.sub.3)--CCl.sub.3 CH.sub.2CH.sub.3 A-71 (S)
CH(CH.sub.3)--CCl.sub.3 H A-72 (S) CH(CH.sub.3)--CCl.sub.3 CH.sub.3
A-73 (S) CH(CH.sub.3)--CCl.sub.3 CH.sub.2CH.sub.3 A-74
CH.sub.2C(CH.sub.3).dbd.CH.sub.2 H A-75
CH.sub.2C(CH.sub.3).dbd.CH.sub.2 CH.sub.3 A-76
CH.sub.2C(CH.sub.3).dbd.CH.sub.2 CH.sub.2CH.sub.3 A-77 cyclopentyl
H A-78 cyclopentyl CH.sub.3 A-79 cyclopentyl CH.sub.2CH.sub.3 A-80
cyclohexyl H A-81 cyclohexyl CH.sub.3 A-82 cyclohexyl
CH.sub.2CH.sub.3 A-83 --(CH.sub.2).sub.4-- A-84 (.+-.)
--(CH.sub.2).sub.2--CH(CH.sub.3)--CH.sub.2-- A-85 (R)
--(CH.sub.2).sub.2--CH(CH.sub.3)--CH.sub.2-- A-86 (S)
--(CH.sub.2).sub.2--CH(CH.sub.3)--CH.sub.2-- A-87
--(CH.sub.2).sub.2--CH(OCH.sub.3)--CH.sub.2-- A-88
--(CH.sub.2).sub.2--CH(CH.sub.2CH.sub.3)--CH.sub.2-- A-89
--(CH.sub.2).sub.2--CH[CH(CH.sub.3).sub.2]--CH.sub.2-- A-90 (.+-.)
--(CH.sub.2).sub.3--CH(CH.sub.3)-- A-91 (.+-.)
--CH(CH.sub.3)--(CH.sub.2).sub.2--CH(CH.sub.3)-- A-92
--CH.sub.2--CH.dbd.CH--CH.sub.2-- A-93 --(CH.sub.2).sub.5-- A-94
(.+-.) --(CH.sub.2).sub.4--CH(CH.sub.3)-- A-95
--(CH.sub.2).sub.2--CH(CH.sub.3)--(CH.sub.2).sub.2-- A-96 (.+-.)
--(CH.sub.2).sub.3--CH(CH.sub.3)--CH.sub.2-- A-97 (R)
--(CH.sub.2).sub.3--CH(CH.sub.3)--CH.sub.2-- A-98 (S)
--(CH.sub.2).sub.3--CH(CH.sub.3)--CH.sub.2-- A-99
--(CH.sub.2).sub.2--C(O[CH.sub.2].sub.2O)--(CH.sub.2).sub.2-- A-100
(CH.sub.2).sub.2 CH.sub.2 A-101
--(CH.sub.2).sub.2--C(O[CH.sub.2].sub.3O)--(CH.sub.2).sub.2-- A-102
--(CH.sub.2).sub.2--CH.dbd.CH--CH.sub.2--
Furthermore with a view to their use, preference is given to the
compounds I compiled in the tables below. Moreover, the groups
mentioned for a substituent in the tables are per se, independently
of the combination in which they are mentioned, a particularly
preferred embodiment of the substituent in question.
##STR00019## Table 181
Compounds of the formulae Ij and Ik in which NR.sup.1R.sup.2 is
4-methylpiperidine and R.sup.3 is methyl and --X--R.sup.a for a
compound corresponds in each case to one row of Table B
Table 182
Compounds of the formulae Ij and Ik in which R.sup.1 is
CH(CH.sub.3).sub.2, R.sup.2 is hydrogen and R.sup.3 is methyl and
--X--R.sup.a for a compound corresponds in each case to one row of
Table B
Table 183
Compounds of the formulae Ij and Ik in which R.sup.1 is
CH.sub.2CF.sub.3, R.sup.2 is hydrogen and R.sup.3 is methyl and
--X--R.sup.a for a compound corresponds in each case to one row of
Table B
Table 184
Compounds of the formulae Ij and Ik in which R.sup.1 is
(R,S)CH(CH.sub.3)CH.sub.2CH.sub.3, R.sup.2 is hydrogen and R.sup.3
is methyl and --X--R.sup.a for a compound corresponds in each case
to one row of Table B
Table 185
Compounds of the formulae Ij and Ik in which R.sup.1 is
(R)CH(CH.sub.3)CH.sub.2CH.sub.3, R.sup.2 is hydrogen and R.sup.3 is
methyl and --X--R.sup.a for a compound corresponds in each case to
one row of Table B
Table 186
Compounds of the formulae Ij and Ik in which R.sup.1 is
(S)CH(CH.sub.3)CH.sub.2CH.sub.3, R.sup.2 is hydrogen and R.sup.3 is
methyl and --X--R.sup.a for a compound corresponds in each case to
one row of Table B
Table 187
Compounds of the formulae Ij and Ik in which R.sup.1 is
(R,S)CH(CH.sub.3)CF.sub.3, R.sup.2 is hydrogen and R.sup.3 is
methyl and --X--R.sup.a for a compound corresponds in each case to
one row of Table B
Table 188
Compounds of the formulae Ij and Ik in which R.sup.1 is
(R)CH(CH.sub.3)CF.sub.3, R.sup.2 is hydrogen and R.sup.3 is methyl
and --X--R.sup.a for a compound corresponds in each case to one row
of Table B
Table 189
Compounds of the formulae Ij and Ik in which R.sup.1 is
(S)CH(CH.sub.3)CF.sub.3, R.sup.2 is hydrogen and R.sup.3 is methyl
and --X--R.sup.a for a compound corresponds in each case to one row
of Table B
Table 190
Compounds of the formulae Ij and Ik in which NR.sup.1R.sup.2 is
4-methylpiperidine and R.sup.3 is chloro and --X--R.sup.a for a
compound corresponds in each case to one row of Table B
Table 191
Compounds of the formulae Ij and Ik in which R.sup.1 is
CH(CH.sub.3).sub.2, R.sup.2 is hydrogen and R.sup.3 is chloro and
--X--R.sup.a for a compound corresponds in each case to one row of
Table B
Table 192
Compounds of the formulae Ij and Ik in which R.sup.1 is
CH.sub.2CF.sub.3, R.sup.2 is hydrogen and R.sup.3 is chloro and
--X--R.sup.a for a compound corresponds in each case to one row of
Table B
Table 193
Compounds of the formulae Ij and Ik in which R.sup.1 is
(R,S)CH(CH.sub.3)CH.sub.2CH.sub.3, R.sup.2 is hydrogen and R.sup.3
is chloro and --X--R.sup.a for a compound corresponds in each case
to one row of Table B
Table 194
Compounds of the formulae Ij and Ik in which R.sup.1 is
(R)CH(CH.sub.3)CH.sub.2CH.sub.3, R.sup.2 is hydrogen and R.sup.3 is
chloro and --X--R.sup.a for a compound corresponds in each case to
one row of Table B
Table 195
Compounds of the formulae Ij and Ik in which R.sup.1 is
(S)CH(CH.sub.3)CH.sub.2CH.sub.3, R.sup.2 is hydrogen and R.sup.3 is
chloro and --X--R.sup.a for a compound corresponds in each case to
one row of Table B
Table 196
Compounds of the formulae Ij and Ik in which R.sup.1 is
(R,S)CH(CH.sub.3)CF.sub.3, R.sup.2 is hydrogen and R.sup.3 is
chloro and --X--R.sup.a for a compound corresponds in each case to
one row of Table B
Table 197
Compounds of the formulae Ij and Ik in which R.sup.1 is
(R)CH(CH.sub.3)CF.sub.3, R.sup.2 is hydrogen and R.sup.3 is chloro
and --X--R.sup.a for a compound corresponds in each case to one row
of Table B
Table 198
Compounds of the formulae Ij and Ik in which R.sup.1 is
(S)CH(CH.sub.3)CF.sub.3, R.sup.2 is hydrogen and R.sup.3 is chloro
and --X--R.sup.a for a compound corresponds in each case to one row
of Table B
Table 199
Compounds of the formulae Ij and Ik in which NR.sup.1R.sup.2 is
4-methylpiperidine and R.sup.3 is methoxy and --X--R.sup.a for a
compound corresponds in each case to one row of Table B
Table 200
Compounds of the formulae Ij and Ik in which R.sup.1 is
CH(CH.sub.3).sub.2, R.sup.2 is hydrogen and R.sup.3 is methoxy and
--X--R.sup.a for a compound corresponds in each case to one row of
Table B
Table 201
Compounds of the formulae Ij and Ik in which R.sup.1 is
CH.sub.2CF.sub.3, R.sup.2 is hydrogen and R.sup.3 is methoxy and
--X--R.sup.a for a compound corresponds in each case to one row of
Table B
Table 202
Compounds of the formulae Ij and Ik in which R.sup.1 is
(R,S)CH(CH.sub.3)CH.sub.2CH.sub.3, R.sup.2 is hydrogen and R.sup.3
is methoxy and --X--R.sup.a for a compound corresponds in each case
to one row of Table B
Table 203
Compounds of the formulae Ij and Ik in which R.sup.1 is
(R)CH(CH.sub.3)CH.sub.2CH.sub.3, R.sup.2 is hydrogen and R.sup.3 is
methoxy and --X--R.sup.a for a compound corresponds in each case to
one row of Table B
Table 204
Compounds of the formulae Ij and Ik in which R.sup.1 is
(S)CH(CH.sub.3)CH.sub.2CH.sub.3, R.sup.2is hydrogen and R.sup.3 is
methoxy and --X--R.sup.a for a compound corresponds in each case to
one row of Table B
Table 205
Compounds of the formulae Ij and Ik in which R.sup.1 is
(R,S)CH(CH.sub.3)CF.sub.3, R.sup.2 is hydrogen and R.sup.3 is
methoxy and --X--R.sup.a for a compound corresponds in each case to
one row of Table B
Table 206
Compounds of the formulae Ij and Ik in which R.sup.1 is
(R)CH(CH.sub.3)CF.sub.3, R.sup.2 is hydrogen and R.sup.3 is methoxy
and --X--R.sup.a for a compound corresponds in each case to one row
of Table B
Table 207
Compounds of the formulae Ij and Ik in which R.sup.1 is
(S)CH(CH.sub.3)CF.sub.3, R.sup.2 is hydrogen and R.sup.3 is methoxy
and --X--R.sup.a for a compound corresponds in each case to one row
of Table B
Table 208
Compounds of the formulae Ij and Ik in which NR.sup.1R.sup.2 is
4-methylpiperidine and R.sup.3 is cyano and --X--R.sup.a for a
compound corresponds in each case to one row of Table B
Table 209
Compounds of the formulae Ij and Ik in which R.sup.1 is
CH(CH.sub.3).sub.2, R.sup.2 is hydrogen and R.sup.3 is cyano and
--X--R.sup.a for a compound corresponds in each case to one row of
Table B
Table 210
Compounds of the formulae Ij and Ik in which R.sup.1 is
CH.sub.2CF.sub.3, R.sup.2 is hydrogen and R.sup.3is cyano and
--X--R.sup.a for a compound corresponds in each case to one row of
Table B
Table 211
Compounds of the formulae Ij and Ik in which R.sup.1 is
(R,S)CH(CH.sub.3)CH.sub.2CH.sub.3, R.sup.2is hydrogen and R.sup.3
is cyano and --X--R.sup.a for a compound corresponds in each case
to one row of Table B
Table 212
Compounds of the formulae Ij and Ik in which R.sup.1 is
(R)CH(CH.sub.3)CH.sub.2CH.sub.3, R.sup.2 is hydrogen and R.sup.3 is
cyano and --X--R.sup.a for a compound corresponds in each case to
one row of Table B
Table 213
Compounds of the formulae Ij and Ik in which R.sup.1 is
(S)CH(CH.sub.3)CH.sub.2CH.sub.3, R.sup.2 is hydrogen and R.sup.3 is
cyano and --X--R.sup.a for a compound corresponds in each case to
one row of Table B
Table 214
Compounds of the formulae Ij and Ik in which R.sup.1 is
(R,S)CH(CH.sub.3)CF.sub.3, R.sup.2 is hydrogen and R.sup.3 is cyano
and --X--R.sup.a for a compound corresponds in each case to one row
of Table B
Table 215
Compounds of the formulae Ij and Ik in which R.sup.1 is
(R)CH(CH.sub.3)CF.sub.3, R.sup.2 is hydrogen and R.sup.3 is cyano
and --X--R.sup.a for a compound corresponds in each case to one row
of Table B
Table 216
Compounds of the formulae Ij and Ik in which R.sup.1 is
(S)CH(CH.sub.3)CF.sub.3, R.sup.2 is hydrogen and R.sup.3 is cyano
and --X--R.sup.a for a compound corresponds in each case to one row
of Table B
TABLE-US-00002 TABLE B No. X R.sup.a B-1 --(C.dbd.O)-- H B-2
CH.sub.3 B-3 CH.sub.2CH.sub.3 B-4 CH.sub.2CH.sub.2CH.sub.3 B-5
CH.sub.2CH(CH.sub.3).sub.2 B-6 CH.sub.2C(CH.sub.3).sub.3 B-7 --O--
H B-8 CH.sub.3 B-9 CH.sub.2CH.sub.3 B-10 CH.sub.2CH.sub.2CH.sub.3
B-11 CH.sub.2CH(CH.sub.3).sub.2 B-12 CH.sub.2C(CH.sub.3).sub.3 B-13
--(C.dbd.O)--O-- H B-14 CH.sub.3 B-15 CH.sub.2CH.sub.3 B-16
CH.sub.2CH.sub.2CH.sub.3 B-17 CH.sub.2CH(CH.sub.3).sub.2 B-18
CH.sub.2C(CH.sub.3).sub.3 B-19 --NH-- H B-20 CH.sub.3 B-21
CH.sub.2CH.sub.3 B-22 CH.sub.2CH.sub.2CH.sub.3 B-23
CH.sub.2CH(CH.sub.3).sub.2 B-24 CH.sub.2C(CH.sub.3).sub.3 B-25
--(C.dbd.O)--NH-- H B-26 CH.sub.3 B-27 CH.sub.2CH.sub.3 B-28
CH.sub.2CH.sub.2CH.sub.3 B-29 CH.sub.2CH(CH.sub.3).sub.2 B-30
CH.sub.2C(CH.sub.3).sub.3 B-31 direct bond H B-32 CH.sub.3 B-33
CH.sub.2CH.sub.3 B-34 CH.sub.2CH.sub.2CH.sub.3 B-35
CH.sub.2CH(CH.sub.3).sub.2 B-36 CH.sub.2C(CH.sub.3).sub.3 B-37
CH.sub.2OH B-38 CH.sub.2CH.sub.2OH B-39 CH.sub.2CH.sub.2CH.sub.2OH
B-40 CH.sub.2CH.sub.2CH.sub.2CH.sub.2OH B-41 CH.sub.2OCH.sub.3 B-42
CH.sub.2CH.sub.2OCH3 B-43 CH.sub.2CH.sub.2CH.sub.2OCH.sub.3 B-44
CH.sub.2CH.sub.2CH.sub.2CH.sub.2OCH.sub.3 B-45
CH.sub.2OCH.sub.2CH.sub.3 B-46 CH.sub.2CH.sub.2OCH.sub.2CH.sub.3
B-47 CH.sub.2CH.sub.2CH.sub.2OCH.sub.2CH.sub.3 B-48
CH.sub.2NH.sub.2 B-49 CH.sub.2CH.sub.2NH.sub.2 B-50
CH.sub.2CH.sub.2CH.sub.2NH.sub.2 B-51 CH.sub.2NHCH.sub.3 B-52
CH.sub.2CH.sub.2NHCH.sub.3 B-53 CH.sub.2CH.sub.2CH.sub.2NHCH.sub.3
B-54 CH.sub.2NHCH.sub.2CH.sub.3 B-55
CH.sub.2CH.sub.2NHCH.sub.2CH.sub.3 B-56
CH.sub.2CH.sub.2CH.sub.2NHCH.sub.2CH.sub.3 B-57
CH.sub.2N(CH.sub.3).sub.2 B-58 CH.sub.2SH B-59 CH.sub.2CH.sub.2SH
B-60 CH.sub.2CH.sub.2CH.sub.2SH B-61 CH.sub.2SCH.sub.3 B-62
CH.sub.2CH.sub.2SCH.sub.3 B-63 CH.sub.2CH.sub.2CH.sub.2SCH.sub.3
B-64 CH.sub.2SCH.sub.2CH.sub.3 B-65
CH.sub.2CH.sub.2SCH.sub.2CH.sub.3 B-66
CH.sub.2CH.sub.2CH.sub.2SCH.sub.2CH.sub.3 B-67 CH(OCH.sub.3).sub.2
B-68 CH.sub.2CH(OCH.sub.3).sub.2 B-69
CH.sub.2CH.sub.2CH(OCH.sub.3).sub.2 B-70 ##STR00020## B-71
##STR00021## B-72 ##STR00022## B-73 ##STR00023## B-74 ##STR00024##
B-75 ##STR00025## B-76 CH.dbd.CH.sub.2 B-77 CH.dbd.CH.sub.2CH.sub.3
B-78 CH.sub.2CH.dbd.CH.sub.2 B-79 CH.sub.2CH.sub.2CH.dbd.CH.sub.2
B-80 CH.sub.2C.ident.CH B-81 CH.sub.2CH.sub.2C.ident.CH
The compounds I are suitable as fungicides. They are distinguished
by an outstanding effectiveness against a broad spectrum of
phytopathogenic fungi, especially from the classes of the
Ascomycetes, Deuteromycetes, Oomycetes and Basidiomycetes. Some are
systemically effective and they can be used in plant protection as
foliar and soil fungicides.
They are particularly important in the control of a multitude of
fungi on various cultivated plants, such as wheat, rye, barley,
oats, rice, corn, grass, bananas, cotton, soybean, coffee, sugar
cane, vines, fruits and ornamental plants, and vegetables, such as
cucumbers, beans, tomatoes, potatoes and cucurbits, and on the
seeds of these plants.
They are especially suitable for controlling the following plant
diseases: Alternaria species on fruit and vegetables, Bipolaris and
Drechslera species on cereals, rice and lawns, Blumeria graminis
(powdery mildew) on cereals, Botrytis cinerea (gray mold) on
strawberries, vegetables, ornamental plants and grapevines,
Erysiphe cichoracearum and Sphaerotheca fuliginea on cucurbits,
Fusarium and Verticillium species on various plants, Mycosphaerella
species on cereals, bananas and peanuts, Phytophthora infestans on
potatoes and tomatoes, Plasmopara viticola on grapevines,
Podosphaera leucotricha on apples, Pseudocercosporella
herpotrichoides on wheat and barley, Pseudoperonospora species on
hops and cucumbers, Puccinia species on cereals, Pyricularia oryzae
on rice, Rhizoctonia species on cotton, rice and lawns, Septoria
tritici and Stagonospora nodorum on wheat, Uncinula necator on
grapevines, Ustilago species on cereals and sugar cane, and
Venturia species (scab) on apples and pears.
The compounds I are also suitable for controlling harmful fungi,
such as Paecilomyces variotii, in the protection of materials (for
example wood, paper, paint dispersions, fibers or fabrics) and in
the protection of stored products.
The compounds I are employed by treating the fungi or the plants,
seeds, materials or soil to be protected against fungal attack with
a fungicidally effective amount of the active compounds. The
application can be carried out both before and after the infection
of the materials, plants or seeds by the fungi.
The fungicidal compositions generally comprise between 0.1 and 95%,
preferably between 0.5 and 90%, by weight of active compound.
When employed in plant protection, the amounts applied are,
depending on the kind of effect desired, between 0.01 and 2.0 kg of
active compound per ha.
In seed treatment, amounts of active compound of 0.001 to 0.1 g,
preferably 0.01 to 0.05 g, per kilogram of seed are generally
necessary.
When used in the protection of materials or stored products, the
amount of active compound applied depends on the kind of
application area and on the desired effect. Amounts customarily
applied in the protection of materials are, for example, 0.001 g to
2 kg, preferably 0.005 g to 1 kg, of active compound per cubic
meter of treated material.
The compounds I can be converted to the customary formulations, for
example solutions, emulsions, suspensions, dusts, powders, pastes
and granules. The application form depends on the particular
intended use; it should in each case ensure a fine and uniform
distribution of the compound according to the invention.
The formulations are prepared in a known manner, for example by
extending the active compound with solvents and/or carriers, if
desired using emulsifiers and dispersants. Solvents/auxiliaries
which are suitable are essentially:
water, aromatic solvents (for example Solvesso products, xylene),
paraffins (for example mineral oil fractions), alcohols (for
example methanol, butanol, pentanol, benzyl alcohol), ketones (for
example cyclohexanone, gamma-butyrolactone), pyrrolidones (NMP,
NOP), acetates (glycol diacetate), glycols, fatty acid
dimethylamides, fatty acids and fatty acid esters. In principle,
solvent mixtures may also be used. carriers such as ground natural
minerals (for example kaolins, clays, talc, chalk) and ground
synthetic minerals (for example highly disperse silica, silicates);
emulsifiers such as nonionic and anionic emulsifiers (for example
polyoxyethylene fatty alcohol ethers, alkylsulfonates and
arylsulfonates) and dispersants such as lignosulfite waste liquors
and methylcellulose.
Suitable surfactants are alkali metal, alkaline earth metal and
ammonium salts of lignosulfonic acid, naphthalenesulfonic acid,
phenolsulfonic acid, dibutylnaphthalenesulfonic acid,
alkylarylsulfonates, alkyl sulfates, alkylsulfonates, fatty alcohol
sulfates, fatty acids and sulfated fatty alcohol glycol ethers,
furthermore condensates of sulfonated naphthalene and naphthalene
derivatives with formaldehyde, condensates of naphthalene or of
naphthalenesulfonic acid with phenol and formaldehyde,
polyoxyethylene octylphenyl ether, ethoxylated isooctylphenol,
octylphenol, nonylphenol, alkylphenyl polyglycol ethers,
tributylphenyl polyglycol ether, tristearylphenyl polyglycol ether,
alkylaryl polyether alcohols, alcohol and fatty alcohol/ethylene
oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl
ethers, ethoxylated polyoxypropylene, lauryl alcohol polyglycol
ether acetal, sorbitol esters, lignosulfite waste liquors and
methylcellulose.
Substances which are suitable for the preparation of directly
sprayable solutions, emulsions, pastes or oil dispersions are
mineral oil fractions of medium to high boiling point, such as
kerosene or diesel oil, furthermore coal tar oils and oils of
vegetable or animal origin, aliphatic, cyclic and aromatic
hydrocarbons, for example toluene, xylene, paraffin,
tetrahydronaphthalene, alkylated naphthalenes or their derivatives,
methanol, ethanol, propanol, butanol, cyclohexanol, cyclohexanone,
isophorone, strongly polar solvents, for example dimethyl
sulfoxide, N-methylpyrrolidone and water.
Powders, materials for spreading and dustable products can be
prepared by mixing or concomitantly grinding the active substances
with a solid carrier.
Granules, for example coated granules, impregnated granules and
homogeneous granules, can be prepared by binding the active
compounds to solid carriers. Examples of solid carriers are mineral
earths such as silica gels, silicates, talc, kaolin, attaclay,
limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous
earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground
synthetic materials, fertilizers, such as, for example, ammonium
sulfate, ammonium phosphate, ammonium nitrate, ureas, and products
of vegetable origin, such as cereal meal, tree bark meal, wood meal
and nutshell meal, cellulose powders and other solid carriers.
In general, the formulations comprise from 0.01 to 95% by weight,
preferably from 0.1 to 90% by weight, of the active compound. The
active compounds are employed in a purity of from 90% to 100%,
preferably 95% to 100% (according to NMR spectrum).
The following are examples of formulations:
1. Products for Dilution with Water
A) Water-Soluble Concentrates (SL)
10 parts by weight of a compound according to the invention are
dissolved in water or in a water-soluble solvent. As an
alternative, wetters or other auxiliaries are added. The active
compound dissolves upon dilution with water.
B) Dispersible Concentrates (DC)
20 parts by weight of a compound according to the invention are
dissolved in cyclohexanone with addition of a dispersant, for
example polyvinylpyrrolidone. Dilution with water gives a
dispersion.
C) Emulsifiable Concentrates (EC)
15 parts by weight of a compound according to the invention are
dissolved in xylene with addition of calcium
dodecylbenzenesulfonate and castor oil ethoxylate (in each case 5%
strength). Dilution with water gives an emulsion.
D) Emulsions (EW, EO)
40 parts by weight of a compound according to the invention are
dissolved in xylene with addition of calcium
dodecylbenzenesulfonate and castor oil ethoxylate (in each case 5%
strength). This mixture is introduced into water by means of an
emulsifier (Ultraturvax) and made into a homogeneous emulsion.
Dilution with water gives an emulsion.
E) Suspensions (SC, OD)
In an agitated ball mill, 20 parts by weight of a compound
according to the invention are comminuted with addition of
dispersants, wetters and water or an organic solvent to give a fine
active compound suspension. Dilution with water gives a stable
suspension of the active compound.
F) Water-Dispersible Granules and Water-Soluble Granules (WG,
SG)
50 parts by weight of a compound according to the invention are
ground finely with addition of dispersants and wetters and made
into water-dispersible or water-soluble granules by means of
technical appliances (for example extrusion, spray tower, fluidized
bed). Dilution with water gives a stable dispersion or solution of
the active compound.
G) Water-Dispersible Powders and Water-Soluble Powders (WP, SP)
75 parts by weight of a compound according to the invention are
ground in a rotor-stator mill with addition of dispersants, wetters
and silica gel. Dilution with water gives a stable dispersion or
solution of the active compound.
2. Products to be Applied Undiluted
H) Dusts (DP)
5 parts by weight of a compound according to the invention are
ground finely and mixed intimately with 95% of finely divided
kaolin. This gives a dustable product.
I) Granules (GR, FG, GG, MG)
0.5 part by weight of a compound according to the invention is
ground finely and associated with 95.5% carriers. Customary methods
are extrusion, spray-drying or the fluidized bed. This gives
granules to be applied undiluted.
J) ULV Solutions (UL)
10 parts by weight of a compound according to the invention are
dissolved in an organic solvent, for example xylene. This gives a
product to be applied undiluted.
The active compounds can be used as such, in the form of their
formulations or of the application forms prepared therefrom, e.g.
in the form of directly sprayable solutions, powders, suspensions
or dispersions, emulsions, oil dispersions, pastes, dustable
products, preparations for broadcasting or granules, by spraying,
atomizing, dusting, broadcasting or watering. The application forms
depend entirely on the intended uses; they should always ensure the
finest possible dispersion of the active compounds according to the
invention.
Aqueous application forms can be prepared from emulsifiable
concentrates, pastes or wettable powders (spray powders, oil
dispersions) by addition of water. To prepare emulsions, pastes or
oil dispersions, the substances can be homogenized in water, as
such or dissolved in an oil or solvent, by means of wetting agents,
tackifiers, dispersants or emulsifiers. However, it is also
possible to prepare concentrates comprising active substance,
wetting agent, tackifier, dispersant or emulsifier and possibly
solvent or oil which are suitable for dilution with water.
The concentrations of active compound in the ready-for-use
preparations can be varied within relatively wide ranges. In
general, they are between 0.0001 and 10%, preferably between 0.01
and 1%.
The active compounds can also be used with great success in the
ultra-low volume (ULV) process, it being possible to apply
formulations with more than 95% by weight of active compound or
even the active compound without additives.
Oils of various types, wetting agents, adjuvants, herbicides,
fungicides, other pesticides and bactericides can be added to the
active compounds, if need be also not until immediately before use
(tank mix). These agents can be added to the preparations according
to the invention in a weight ratio of 1:10 to 10:1.
The preparations according to the invention can, in the application
form as fungicides, also be present together with other active
compounds, e.g. with herbicides, insecticides, growth regulators,
fungicides or also with fertilizers. On mixing the compounds I or
the preparations comprising them in the application form as
fungicides with other fungicides, in many cases an expansion of the
fungicidal spectrum of activity is obtained.
The following list of fungicides, with which the compounds
according to the invention can be used in conjunction, is intended
to illustrate the possible combinations but does not limit them:
acylalanines, such as benalaxyl, metalaxyl, ofurace or oxadixyl,
amine derivatives, such as aldimorph, dodine, dodemorph,
fenpropimorph, fenpropidin, guazatine, iminoctadine, spiroxamine or
tridemorph, anilinopyrimidines, such as pyrimethanil, mepanipyrim
or cyprodinyl, antibiotics, such as cycloheximide, griseofulvin,
kasugamycin, natamycin, polyoxin or streptomycin, azoles, such as
bitertanol, bromoconazole, cyproconazole, difenoconazole,
dinitroconazole, epoxiconazole, fenbuconazole, fluquinconazole,
flusilazole, flutriafol, hexaconazole, imazalil, metconazole,
myclobutanil, penconazole, propiconazole, prochloraz,
prothioconazole, tebuconazole, triadimefon, triadimenol,
triflumizole or triticonazole, dicarboximides, such as iprodione,
myclozolin, procymidone or vinclozolin, dithiocarbamates, such as
ferbam, nabam, maneb, mancozeb, metam, metiram, propineb,
polycarbamate, thiram, ziram or zineb, heterocyclic compounds, such
as anilazine, benomyl, boscalid, carbendazim, carboxin,
oxycarboxin, cyazofamid, dazomet, dithianon, famoxadone,
fenamidone, fenarimol, fuberidazole, flutolanil, furametpyr,
isoprothiolane, mepronil, nuarimol, probenazole, proquinazid,
pyrifenox, pyroquilon, quinoxyfen, silthiofam, thiabendazole,
thifluzamide, thiophanate-methyl, tiadinil, tricyclazole or
triforine, copper fungicides, such as Bordeaux mixture, copper
acetate, copper oxychloride or basic copper sulfate, nitrophenyl
derivatives, such as binapacryl, dinocap, dinobuton or
nitrophthal-isopropyl, phenylpyrroles, such as fenpiclonil or
fludioxonil, sulfur, other fungicides, such as
acibenzolar-S-methyl, benthiavalicarb, carpropamid, chlorothalonil,
cyflufenamid, cymoxanil, dazomet, diclomezine, diclocymet,
diethofencarb, edifenphos, ethaboxam, fenhexamid, fentin acetate,
fenoxanil, ferimzone, fluazinam, fosetyl, fosetyl-aluminum,
iprovalicarb, hexachlorobenzene, metrafenone, pencycuron,
propamocarb, phthalide, tolclofos-methyl, quintozene or zoxamide,
strobilurins, such as azoxystrobin, dimoxystrobin, fluoxastrobin,
kresoxim-methyl, metominostrobin, orysastrobin, picoxystrobin,
pyraclostrobin or trifloxystrobin, sulfenic acid derivatives, such
as captafol, captan, dichlofluanid, folpet or tolylfluanid,
cinnamides and analogous compounds, such as dimethomorph,
flumetover or flumorph.
SYNTHESIS EXAMPLES
Example 1
Preparation of
4-chloro-6-((S)-2,2,2-trifluoro-1-methylethylamino)-5-(2,4,6-trifluorophe-
nyl)-pyrimidine-2-carboxamide [I-5]
##STR00026##
5.0 g of
4-chloro-6-((S)-2,2,2-trifluoro-1-methylethylamino)-5-(2,4,6-tri-
fluorophenyl)-pyrimidine-2-carbonitrile (see WO 03/04993, pages 28
and 29) were initially charged in 5 ml of DMSO, 344 mg of
K.sub.2CO.sub.3 were added and the mixture was cooled to 10.degree.
C. 1.4 ml of 30% strength H.sub.2O.sub.2 were then added. The
mixture was stirred in an ice bath for 5 min and then at room
temperature for another 30 min. The reaction mixture was introduced
into 150 ml of water. During the addition, the amide precipitated
out. The amide was filtered off, washed and dried under high
vacuum. This gave 4.7 g of the beige title compound of m.p.
157-162.degree. C.
Example 2
Preparation of
4-chloro-6-((S)-2,2,2-trifluoro-1-methylethylamino)-5-(2,4,6-trifluorophe-
nyl)-pyrimidine-2-carboxylic acid [I-11]
##STR00027##
1.5 g of
4-chloro-6-((S)-2,2,2-trifluoro-1-methylethylamino)-5-(2,4,6-tri-
fluorophenyl)-pyrimidine-2-carbonitrile (see WO 03/04993, pages 28
and 29) were dissolved in 5 ml of conc. H.sub.2SO.sub.4, and the
mixture was stirred at 110.degree. C. for 20 min. The reaction
mixture was introduced into 100 ml of ice-water, and during the
addition the acid precipitated out. The acid was filtered off,
washed with water and dried under high vacuum. This gave 1.5 g of
the yellow title compound.
.sup.1H-NMR (CDCl.sub.3, ppm): 1.4 (d, CH.sub.3), 4.85 (d, NH),
5.60-5.80 (m, CH), 6.90-7.00 (m, CH), 10.5 (s (broad), OH).
Example 3
Preparation of
N-tert.-butyl-4-chloro-6-((S)-2,2,2-trifluoro-1-methyl-ethylamino)-5-(2,4-
,6-trifluorophenyl)pyrimidine-2-carboxamide [I-10]
##STR00028## a) 1.5 g of the acid (Example 2) were added to 5 ml of
thionyl chloride at 40.degree. C. The reaction mixture was stirred
until the evolution of gas had ceased. Toluene was added to the
mixture and the solvent and excess thionyl chloride were distilled
off completely. This gave 1.6 g of a dark-green oil. b) 38 mg of
tert-butylamine and 58 mg of triethylamine were initially charged
in 7 ml of THF at 0.degree. C., and 200 mg of the acid chloride
prepared beforehand, dissolved in 2 ml of THF, were added. The
reaction mixture was stirred at room temperature for 12 h. The
reaction mixture was concentrated using a rotary evaporator, taken
up in methyl tert-butyl ether and washed with water. The organic
phase was removed, dried over MgSO.sub.4 and concentrated. The
crude product was purified by preparative HPLC. This gave 21 mg of
the yellow title compound of m.p. 49-54.degree. C.
Example 4
Preparation of
N-acetyl-4-chloro-6-((S)-2,2,2-trifluoro-1-methylethylamino)-5-(2,4,6-tri-
fluorophenyl)-pyrimidine-2-carboximide [I-12]
##STR00029##
With ice bath cooling, 150 mg of amide (Example 1) in 10 ml of THF
were reacted with 20 mg of sodium hydride, and the mixture was
stirred for 30 min. 35 mg of acetyl chloride, dissolved in 1 ml of
THF, were added slowly. The reaction mixture was stirred at room
temperature for 30 min. Ice-water was then added to the reaction
mixture, and the mixture was extracted with dichloromethane. The
combined organic phases were dried over Mg.sub.2SO.sub.4 and
concentrated using a rotary evaporator. This gave 65 mg of the
red-brown title compound of m.p. 58-65.degree. C.
Example 5
Preparation of isopropyl
4-chloro-6-((S)-2,2,2-trifluoro-1-methylethylamino)-5-(2,4,6-trifluorophe-
nyl)pyrimidine-2-carboxylate [V-3]
##STR00030##
At room temperature, 22 g of
4-chloro-6-((S)-2,2,2-trifluoro-1-methylethylamino)-5-(2,4,6-trifluorophe-
nyl)pyrimidine-2-carbonitrile were dissolved in 210 ml of
isopropanol. Over a period of 30 min, HCl gas was introduced into
the solution, and the mixture was then stirred at reflux for 96 h.
The mixture was concentrated, water was added, followed by a
top-layer of ethyl acetate, and the mixture was made alkaline using
sodium carbonate. The ethyl acetate phase was dried with magnesium
sulfate and concentrated using a rotary evaporator. This gave 21.4
g of a colorless solid.
Yield: 83.8%. m.p.: 146-147.degree. C.
With appropriate modification of the starting materials, the
procedures given in the synthesis examples above were used to
obtain further compounds I. The compounds obtained in this manner
are listed in the table 1 below, together with physical data.
TABLE-US-00003 TABLE IA 1A ##STR00031## m.p. .sup.1H-NMR No.
R.sup.aX R.sup.1 R.sup.2 L.sub.n [.degree. C.] [CDCl.sub.3, ppm]
I-1 H (R,S)- H 2,4,6- 0.80-0.90 (m, 2CH.sub.3),
CH(CH.sub.3)CH(CH.sub.3).sub.2 trifluoro 1.15 (d, CH5), 1.75-1.85
(m, CH), 4.25-4.30 (m, CH), 4.60 (s, NH), 6.75 (s, NH), 6.80-6.90
(m, 2CH), 7.70 (s, NH) I-2 H
--(CH.sub.2).sub.2CH(CH.sub.3)(CH.sub.2).sub.2-- 2,4,6- 116-128
trifluoro I-3 H --CH(CH.sub.3).sub.2 H 2-chloro-6- 208-210 fluoro
I-4 NH.sub.2 --CH(CH.sub.3).sub.2 H 2-chloro-6- 103-108 fluoro I-5
H (S)--CH(CH.sub.3)CF.sub.3 H 2,4,6- 157-162 trifluoro I-6 NH.sub.2
(S)--CH(CH.sub.3)CF.sub.3 H 2,4,6- 59-65 trifluoro I-7 H
--CH.sub.2C.dbd.CH.sub.2 CH.sub.2C.dbd.CH.sub.2 2,4,6- 134-141
trifluoro I-8 CH.sub.3 --CH.sub.2C.dbd.CH.sub.2
CH.sub.2C.dbd.CH.sub.2 2,4,6- 52-58 trifluoro I-9
--N(CH.sub.3).sub.2 (S)--CH(CH.sub.3)CF.sub.3 H 2,4,6- 39-45
trifluoro I-10 --C(CH.sub.3).sub.3 (S)--CH(CH.sub.3)CF.sub.3 H
2,4,6- 49-54 trifluoro I-11 --OH (S)--CH(CH.sub.3)CF.sub.3 H 2,4,6-
1.4 (d, CH3), 4.85 trifluoro (d, NH), 5.60-5.80 (m, CH), 6.90-7.00
(m, CH), 10.5 (s(broad), OH) I-12 (C.dbd.O)CH.sub.3
(S)--CH(CH.sub.3)CF.sub.3 H 2,4,6- 58-65 trifluoro I-13 H
--CH(CH.sub.3)CF.sub.3 H 2,4,6- 222-224 trifluoro I-14 --CH.sub.3
(S)--CH(CH.sub.3)CF.sub.3 H 2,4,6- 1.25 (d, 3H), 2.9 (d, 3H),
triftuoro 5.25 (m, 2H), 6.75 (m, 2H), 7.8 (s, 1H) I-15 H
--CH.sub.2--COOH H 2,4,6- 227-228 trifluoro I-16 H (R)
--CH(CH.sub.3)CH(CH.sub.3).sub.2 H 2,4,6- 0.75 (m, 6H), 1.1 (m,
trifluoro 3H), 1.75 (m, 1H), 4.2 (m, 1H), 4.4 (m, 1H), 5.8 (s, 1H),
7.25 (m, 2H), 7.4 (m, 1H), 7.6 (s, 1H) I-17 H --CH(CH.sub.3).sub.2
H 2-chloro-4- 141-150 fluoro I-18 H --CH.sub.2--C.sub.6H.sub.5 H
2-chloro-4- 48-56 fluoro I-19 H (R)
--CH(CH.sub.3)CH(CH.sub.3).sub.2 H 2,4- 0.75 (m, 6H), 1.1 (m,
difluoro 3H), 1.75 (m, 1H), 4.2 (m, 1H), 4.5 (m, 1H), 5.85 (s, 1H),
7.1 (m, 2H), 7.3 (m, 1H), 7.6 (s, 1H) I-20 H
--CH.sub.2--C.sub.6H.sub.5 H 2,4- 53-58 difluoro I-21 H
--CH(CH.sub.3).sub.2 H 2,4- 172-176 difluoro I-22 H
--(CH.sub.2).sub.2CH(CH.sub.3)(CH.sub.2).sub.2-- 2,4- 50-63
difluoro I-23 H (S)--CH(CH.sub.3)CH(CH.sub.3).sub.2 H 2,4- 99-105
difluoro I-24 H (S)--CH(CH.sub.3)CH(CH.sub.3).sub.2 H 2-chloro-4-
79-88 fluoro I-25 H
--(CH.sub.2).sub.2CH(CH.sub.3)(CH.sub.2).sub.2-- 2,6- 173-175
difluoro I-26 H --(CH.sub.2).sub.2CH(CH.sub.3)(CH.sub.2).sub.2--
2-chloro-4- 175-17- 7 fluoro I-27 H (S)--CH(CH.sub.3)CF.sub.3 H
2,6- 206-208 difluoro I-28 H (S)--CH(CH.sub.3)CH(CH.sub.3).sub.2 H
2,6- 128-130 difluoro I-29 H (S)--CH(CH.sub.3)CF.sub.3 H
2-chloro-4- 165-167 fluoro I-30 (C.dbd.O)CH.sub.3
--(CH.sub.2).sub.2CH(CH.sub.3)(CH.sub.2).sub.2-- 2-- chloro-4- 0.9
(d, 3H), 1.0 (m, fluoro 2H), 2.6 (s, 3H), 4.0 (m, 2H), 7.1 (m, 1H),
7.25 (m, 2H), 10.0 (s, 1H) I-31 H
(S)--CH(CH.sub.3)CH(CH.sub.3).sub.2 H 2-chloro-4- 84-88 methoxy
I-32 H (S)--CH(CH.sub.3)CF.sub.3 H 2,4,6- 1.4 (m, 3H), 3.9 (s,
trifluoro 3H), 5.0 (d, 1H), 5.25 (m, 1H), 6.8 (m, 2H) I-33
(C.dbd.O)CH.sub.3 --(CH.sub.2).sub.2CH(CH.sub.3)(CH.sub.2).sub.2--
2,- 6-difluoro 0.9 (d, 3H), 1.0 (m, 2H), 1.6 (s, 3H), 2.8 (s, 3H),
4.0 (m, 2H), 7.0 (m, 2H), 7.45 (m, 1H), 10.0 (s, 1H)
TABLE-US-00004 TABLE VA VA ##STR00032## m.p. .sup.1H-NMR No. R'
R.sup.1 R.sup.2 L.sub.n [.degree. C.] [CDCl.sub.3, ppm] V-1
CH.sub.3 (S)--CH(CH.sub.3)CF.sub.3 H 2,4,6- 1.3 (d, 3H), 4.0 (s,
3H), trifluoro 4.6 (d, NH), 5.25 (m, 1H), 6.9 (m, 2H) V-2
--CH(CH.sub.3).sub.2 --CH.sub.2C.dbd.CH.sub.2
--CH.sub.2C.dbd.CH.sub.2- 2,4,6- 53-57 trifluoro V-3
--CH(CH.sub.3).sub.2 (S)--CH(CH.sub.3)CF.sub.3 H 2,4,6- 146-147
trifluoro V-4 --CH.sub.2CH.sub.3 (3) --CH(CH.sub.3)CF.sub.3 H
2,4,6- 1.35 (d, 3H), 1.45 (t, 3H), trifluoro 4.5 (q, 2H), 4.6 (d,
NH), 5.3 (m, CH), 6.9 (m, 2H) V-5 --(CH.sub.2).sub.2CH.sub.3 (3)
--CH(CH.sub.3)CF.sub.3 H 2,4,6- 100-105 trifluoro V-6
--CH(CH.sub.3).sub.2 --CH.sub.2CF.sub.3 H 2,4,6- 115-118 trifluoro
V-7 --(CH.sub.2).sub.3CH.sub.3 (S)--CH(CH.sub.3)CF.sub.3 H 2,4,6-
71-75 trifluoro V-8 --(CH.sub.2).sub.4CH.sub.3 (3)
--CH(CH.sub.3)CF.sub.3 H 2,4,6- 82-88 trifluoro V-9
--(CH.sub.2).sub.5CH.sub.3 (S)--CH(CH.sub.3)CF.sub.3 H 2,4,6- 57-60
trifluoro V-10 --CH.sub.2CF.sub.3 (S)--CH(CH.sub.3)CF.sub.3 H
2,4,6- 1.35 (d, 3H), 4.7 (d, NH), trifluoro 4.8 (m, 2H), 5.3 (m,
1H), 6.9 (m, 2H) V-11 --(CH.sub.2).sub.2CH(CH.sub.3).sub.2
(S)--CH(CH.sub.3)CF.sub.3 H 2,4,- 6- 90-93 trifluoro V-12
--CH.sub.2CH(CH.sub.3)-- (S)--CH(CH.sub.3)CF.sub.3 H 2,4,6- 75-81
CH.sub.2CH.sub.3 trifluoro m.p. .sup.1H-NMR No. R.sup.aX R.sup.1
R.sup.2 L.sub.n [.degree. C.] [CDCl.sub.3, ppm] V-13
--CH(CH.sub.3)-- (S)--CH(CH.sub.3)CF.sub.3 2,4,6- 0.9 (t, 3H),
1.3-1.9 (m, (CH.sub.2).sub.2CH.sub.3 trifluoro 13H), 4.55 (d, NH),
5.25 (m, 2H), 6.9 (m, 2H) V-14 --CH(CH.sub.3).sub.2
--(CH.sub.2).sub.2CH(CH.sub.3)(CH.sub.2).sub.2--- 2,4,6- 0.8 (d,
3H), 0.9 (m, 2H), trifluoro 1.4 (d, 6H), 1.5 (m, 3H), 2.7 (t, 2H),
3.9 (d, 2H), 5.2 (m, CH), 6.7 (m, 2H) V-15 --CH(CH.sub.3)--
(S)--CH(CH.sub.3)CF.sub.3 H 2,4,6- 1.0 (m, 6H), 1.4 (m 6H),
CH(CH.sub.3).sub.2 trifluoro 2.0 (m, CH), 4.6 (m, NH), 5.0 (m, CH),
5.3 (m, CH), 6.9 (m, 2H) V-16 --CH.sub.2C.dbd.CH.sub.2
(S)--CH(CH.sub.3)CF.sub.3 H 2,4,6- 1.35 (d, 3H), 4.8 (d, 2H),
trifluoro 4.95 (d, 1H), 6.3 (m, 2H), 5.45 (d, 1H), 6.1 (m, 1H), 6.9
(m, 1H) V-17 --(CH.sub.2).sub.2NH.sub.2 (S)--CH(CH.sub.3)CF.sub.3 H
2,4,6- 1.0 (m, 6H), 1.4 (m 6H), trifluoro 2.0 (m, CH), 4.6 (m, NH),
5.0 (m, CH), 5.3 (m, CH), 6.9 (m, 2H) V-18 cyclohexyl
(S)--CH(CH.sub.3)CF.sub.3 H 2,4,6- 1.35 (d, 3H), 4.8 (d, 2H),
trifluoro 4.95 (d, 1H), 6.3 (m, 2H), 5.45 (d, 1H), 6.1 (m, 1H), 6.9
(m, 1H) V-19 --CH.sub.2CH(CH.sub.3).sub.2 (S)--CH(CH.sub.3)CF.sub.3
H 2,4,6- 97-102 trifluoro V-20 --CH(CH.sub.3)CH.sub.2CH.sub.3
(S)--CH(CH.sub.3)CF.sub.3-- H 2,4,6- 1- 45-146 trifluoro V-21
--CH.sub.2C.sub.6H.sub.5 (S)--CH(CH.sub.3)CF.sub.3 H 2,4,6- 1.4 (d,
3H), 4.55 (m, 3H), trifluoro 5.25 (m, 1H), 6.9 (m, 2H), 7.3-7.5 (m,
5H) V-22 cyclopentyl (S)--CH(CH.sub.3)CF.sub.3 H 2,4,6- 114-115
trifluoro V-23 cyclobutyl (S)--CH(CH.sub.3)CF.sub.3 H 2,4,6-
127-129 trifluoro
Examples of the action against harmful fungi
The fungicidal action of the compounds of the formula I was
demonstrated by the following experiments:
The active compounds were prepared separately as a stock solution
with 0.25% by weight of active compound in acetone or DMSO. 1% by
weight of the emulsifier Uniperol.RTM. EL (wetting agent having
emulsifying and dispersing action based on ethoxylated
alkylphenols) was added to this solution. The stock solutions of
the active compounds were diluted with water to the stated
concentration.
USE EXAMPLES
1. Activity Against Late Blight on Tomatoes Caused by Phytophthora
infestans, Protective Treatment
Leaves of potted plants of the cultivar "Goldene Prinzessin" were
sprayed to runoff point with an aqueous suspension having the
concentration of active compound stated below. The next day, the
leaves were infected with an aqueous sporangiophore suspension of
Phytophthora infestans. The plants were then placed in a
water-vapor-saturated chamber at 18-20.degree. C. After 6 days, the
late blight on the untreated, but infected control plants had
developed to such an extent that the infection could be determined
visually in %.
TABLE-US-00005 ##STR00033## infection at 250 ppm of No. R.sup.4
document a.i. (% leaf area) I-5 --(C.dbd.O)NH.sub.2 according to 0
the invention V-3 --(C.dbd.O)--O--CH(CH).sub.3 according to 5 the
invention V1 --(C.dbd.NOCH.sub.3)NH.sub.2 WO 03/043993 80 untreated
80
2. Persistency Against Early Blight on Tomatoes Caused by
Alternaria solani, Protective Treatment
Leaves of potted plants of the cultivar "Goldene Prinzessin" were
sprayed to runoff point with an aqueous suspension having the
concentration of active compound stated below.
To test for persistency, the leaves were infected with an aqueous
spore suspension of Alternaria solani in a 2% strength biomalt
solution having a density of 0.17.times.10.sup.6 spores/ml only
after seven days. The plants were then placed in a
water-vapor-saturated chamber at 20-22.degree. C. After a further 5
days, the disease on the untreated, but infected control plants had
developed to such an extent that the infection could be determined
visually in %.
TABLE-US-00006 ##STR00034## infection at 16 ppm No. R.sup.4
document of a.i. (% leaf area) I-5 (C.dbd.O)NH.sub.2 according to
the 30 invention V1 (C.dbd.NOCH.sub.3)NH.sub.2 WO 03/043993 67
untreated 90
3. Activity Against Gray Mold on Bell Pepper Leaves caused by
Botrytis cinerea, Protective Application
Bell pepper seedlings of the cultivar "Neusiedler Ideal Elite"
were, after 2-3 leaves were well developed, sprayed to runoff point
with an aqueous suspension having the concentration of active
compound stated below. The next day, the treated plants were
inoculated with a spore suspension of Botrytis cinerea which
contained 1.7.times.10.sup.6 spores/ml in a 2% strength aqueous
biomalt solution, The test plants were then placed in a climatized
chamber at 22-24.degree. C., in the dark and at high atmospheric
humidity. After 5 days, the extent of the fungal infection on the
leaves could be determined visually in %.
TABLE-US-00007 ##STR00035## infection at 16 ppm of No. R.sup.4
document a.i. (% leaf area) I-2 --(C.dbd.O)NH.sub.2 according to
the 15 invention V2 --(C.dbd.NOCH.sub.3)NH.sub.2 Example I-186 from
90 WO 03/043993 untreated 100
* * * * *